U.S. patent application number 16/484587 was filed with the patent office on 2020-08-27 for shaping material, resin shaped product, cosmetic container, semiconductor container, and method of producing semiconductor conta.
This patent application is currently assigned to ZEON CORPORATION. The applicant listed for this patent is ZEON CORPORATION. Invention is credited to Eito ARIURA, Ayako KATO, Shinsuke MIYAZAWA, Satoshi YAMADA.
Application Number | 20200269477 16/484587 |
Document ID | / |
Family ID | 1000004841717 |
Filed Date | 2020-08-27 |
![](/patent/app/20200269477/US20200269477A1-20200827-C00001.png)
United States Patent
Application |
20200269477 |
Kind Code |
A1 |
MIYAZAWA; Shinsuke ; et
al. |
August 27, 2020 |
SHAPING MATERIAL, RESIN SHAPED PRODUCT, COSMETIC CONTAINER,
SEMICONDUCTOR CONTAINER, AND METHOD OF PRODUCING SEMICONDUCTOR
CONTAINER
Abstract
A shaping material contains a crystalline alicyclic
structure-containing resin. More specifically, the crystalline
alicyclic structure-containing resin in the shaping material has a
melting point of 200.degree. C. or higher, and content of
chlorobenzene-soluble components in the shaping material is 1,000
ppm or less as an o-dichlorobenzene-equivalent value based on gas
chromatography analysis with o-dichlorobenzene as a standard
substance.
Inventors: |
MIYAZAWA; Shinsuke;
(Chiyoda-ku, Tokyo, JP) ; YAMADA; Satoshi;
(Chiyoda-ku, Tokyo, JP) ; KATO; Ayako;
(Chiyoda-ku, Tokyo, JP) ; ARIURA; Eito;
(Chiyoda-ku, Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ZEON CORPORATION |
Chiyoda-ku Tokyo |
|
JP |
|
|
Assignee: |
ZEON CORPORATION
Chiyoda-ku Tokyo
JP
|
Family ID: |
1000004841717 |
Appl. No.: |
16/484587 |
Filed: |
March 19, 2018 |
PCT Filed: |
March 19, 2018 |
PCT NO: |
PCT/JP2018/010903 |
371 Date: |
August 8, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29C 45/0001 20130101;
B29C 45/0055 20130101; B29C 45/26 20130101 |
International
Class: |
B29C 45/00 20060101
B29C045/00; B29C 45/26 20060101 B29C045/26 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 21, 2017 |
JP |
2017-054948 |
Mar 23, 2017 |
JP |
2017-057534 |
Sep 29, 2017 |
JP |
2017-190293 |
Claims
1. A shaping material comprising a crystalline alicyclic
structure-containing resin, wherein the crystalline alicyclic
structure-containing resin has a melting point of 200.degree. C. or
higher, and content of chlorobenzene-soluble components in the
shaping material is 1,000 ppm or less as an
o-dichlorobenzene-equivalent value based on gas chromatography
analysis with o-dichlorobenzene as a standard substance.
2. The shaping material according to claim 1, wherein the
crystalline alicyclic structure-containing resin is a hydrogenated
dicyclopentadiene ring-opened polymer.
3. The shaping material according to claim 1 used in injection
molding.
4. A resin shaped product obtained through melt shaping of the
shaping material according to claim 1.
5. A cosmetic container that is a shaped item of the shaping
material according to claim 1.
6. A semiconductor container that is a shaped item of the shaping
material according to claim 1.
7. The semiconductor container according to claim 6, having a
degree of crystallinity of 10% or more.
8. A method of producing a semiconductor container comprising: a
purification step of holding a target resin including a crystalline
alicyclic structure-containing resin having a melting point Tm
(.degree. C.) of 200.degree. C. or higher in a purification
temperature range of not lower than 140.degree. C. and not higher
than 300.degree. C. for not less than 0.5 hours and not more than
100 hours to obtain a purified target resin; and a shaping step of
heating a pre-crystallization shaping material including the
purified target resin to a higher temperature than the melting
point Tm (.degree. C.) to melt the pre-crystallization shaping
material and subsequently shaping the pre-crystallization shaping
material while holding the pre-crystallization shaping material in
a crystallization temperature range of not lower than
(Tm-140.degree.) C. and lower than the melting point Tm (.degree.
C.) to cause crystallization.
9. The method of producing a semiconductor container according to
claim 8, wherein content of chlorobenzene-soluble components in the
pre-crystallization shaping material used in the shaping step is
1,000 ppm or less as an o-dichlorobenzene-equivalent value based on
gas chromatography analysis with o-dichlorobenzene as a standard
substance.
Description
TECHNICAL FIELD
[0001] The present disclosure relates to a shaping material, a
resin shaped product, a cosmetic container, a semiconductor
container, and a method of producing a semiconductor container. In
particular, the present disclosure relates to a shaping material
and so forth containing a crystalline alicyclic
structure-containing resin.
BACKGROUND
[0002] Crystalline alicyclic structure-containing resins have been
attracting attention in recent years as materials for various resin
shaped products due to having excellent physical properties such as
heat resistance, mechanical strength, and solvent resistance.
[0003] In one example, Patent Literature (PTL) 1 describes a
polymer composition that contains a crystalline norbornene-based
polymer, an amorphous alicyclic structure-containing polymer, and
so forth, and also describes medical equipment obtained through
shaping of this polymer composition. In this document, coagulation
and direct drying are given as examples of purification methods
that can be used after production of the crystalline
norbornene-based polymer.
[0004] Among crystalline alicyclic structure-containing resins,
polymers that include a large quantity of repeating units derived
from specific monomers such as dicyclopentadiene are known to
generally have high melting points.
[0005] For example, PTL 2 describes a hydrogenated product of a
norbornene-based ring-opened polymer that has a melting point and
also describes an injection molded item thereof. PTL 2 also
discloses that a hydrogenated dicyclopentadiene ring-opened polymer
has a melting point of 272.degree. C.
[0006] Moreover, PTL 3 describes a hydrogenated dicyclopentadiene
ring-opened polymer having syndiotactic stereoregularity and also
describes a crystalline resin composition containing this polymer
and a crystal nucleating agent. PTL 3 also discloses that the
melting point of an actually obtained hydrogenated
dicyclopentadiene ring-opened polymer was 265.degree. C.
[0007] PTL 4 discloses that heat shrinkage and the like of a
stretched film obtained through stretching of a resin film having a
crystalline alicyclic structure-containing resin as a main
component can be controlled by bringing the stretched film into
contact with a hydrocarbon solvent.
[0008] PTL 4 also discloses that when a stretched film having a
hydrogenated dicyclopentadiene ring-opened polymer as a main
component is immersed in toluene or cyclohexane, a value for the
rate of heat shrinkage of the stretched film decreases compared to
that of the stretched film prior to immersion.
[0009] This indicates that in a situation in which crystallization
has proceeded to a certain extent in a resin shaped product
containing a crystalline alicyclic structure-containing resin, the
inclusion of a hydrocarbon solvent therein can cause rearrangement
of polymer chains and allow further progression of
crystallization.
[0010] In recent years, there have been many attempts to obtain a
wide range of shaped products capable of displaying higher
performance than conventionally achieved. In one example, PTL 5
describes an injection molded item for medical applications and a
blow molded item for medical applications that are obtained by
shaping, under specific conditions, a resin composition that
contains 70 weight % to 90 weight % of a norbornene-based polymer
and 10 weight % to 30 weight % of a block copolymer composed of a
hydrogenated styrene-based thermoplastic elastomer. In another
example, PTL 6 describes a food container obtained through shaping
of a hydrogenated norbornene-based ring-opened polymer that
includes a repeating unit derived from 2-norbornene and that has a
melting point within a range of 110.degree. C. to 145.degree. C. In
yet another example, PTL 7 describes a container for a wafer used
in semiconductor production (semiconductor container) wherein at
least one of a main body and a lid of the container is formed by a
shaped product of a cycloolefin resin.
CITATION LIST
Patent Literature
[0011] PTL 1: JP 2011-26614 A
[0012] PTL 2: JP 2002-20464 A
[0013] PTL 3: JP 2015-54885 A
[0014] PTL 4: JP 2016-26909 A
[0015] PTL 5: JP 2015-160399 A
[0016] PTL 6: JP 2008-137671 A
[0017] PTL 7: JP H11-74337 A
SUMMARY
Technical Problem
[0018] Demands relating to shaping materials that have excellent
formability while also having a high melting point and shaped items
that have higher performance than conventionally achieved have been
increasing in recent years. However, the various resins disclosed
in PTL 1 to 7 have not been able to satisfy this need.
[0019] Accordingly, an objective of the present disclosure is to
provide a shaping material that contains a high-melting point resin
and has excellent formability, and also to provide a resin shaped
product, a cosmetic container, and a semiconductor container that
are obtained through shaping of this shaping material.
[0020] In particular, cosmetic containers are normally required to
be hygienic and have excellent safety and stability such that
elution of components of the container does not occur even while in
contact with contents of the container. In addition, the
development of containers having complicated structures,
low-capacity containers, and so forth in recent years has made it
necessary for shaping material used in production of cosmetic
containers to have excellent formability. However, the various
resins disclosed in PTL 1 to 7 have not been able to satisfy this
need.
[0021] Accordingly, another objective of the present disclosure is
to provide a cosmetic container having excellent performance.
[0022] Furthermore, in recent years, it has become desirable to
provide even faster production processes for semiconductor devices
from a viewpoint of improving production yield. For this reason, a
semiconductor container (FOUP: Front Opening Unified Pod) that is
used to transfer a semiconductor wafer in a semiconductor
production process is required to be able to house the
semiconductor wafer after heating thereof in the production
process, even without providing cooling time for the semiconductor
wafer. However, the various resins disclosed in PTL 1 to 7 have not
been able to satisfy this need. Note that a FOUP is a front opening
cassette unified box for transport and storage defined by "SEMI
Standard E47.1".
[0023] Accordingly, another objective of the present disclosure is
to provide a semiconductor container having high heat resistance
and also to provide a method of producing a semiconductor container
that enables good production of this semiconductor container.
Solution to Problem
[0024] The present disclosure aims to advantageously solve the
problems set forth above by disclosing a shaping material
comprising a crystalline alicyclic structure-containing resin,
wherein the crystalline alicyclic structure-containing resin has a
melting point of 200.degree. C. or higher, and content of
chlorobenzene-soluble components in the shaping material is 1,000
ppm or less as an o-dichlorobenzene-equivalent value based on gas
chromatography analysis with o-dichlorobenzene as a standard
substance. A shaping material that contains a crystalline alicyclic
structure-containing resin having a melting point of 200.degree. C.
or higher and in which the content of chlorobenzene-soluble
components is 1,000 ppm or less as set forth above has excellent
formability despite containing a high-melting point resin.
[0025] The "melting point of a crystalline alicyclic
structure-containing resin" can be measured by differential
scanning calorimetry in accordance with JIS K7121. Moreover, the
"content of chlorobenzene-soluble components in a shaping material"
can be measured by a method described in the EXAMPLES section.
[0026] In the presently disclosed shaping material, the crystalline
alicyclic structure-containing resin is preferably a hydrogenated
dicyclopentadiene ring-opened polymer. When the crystalline
alicyclic structure-containing resin is a hydrogenated
dicyclopentadiene ring-opened polymer, it is possible to further
improve heat resistance and chemical resistance of the shaping
material and of a shaped product or the like obtained using the
shaping material.
[0027] The presently disclosed shaping material can suitably be
used in injection molding. Use of the presently disclosed shaping
material in injection molding enables stable production a resin
shaped product in which crystallization has sufficiently
progressed.
[0028] A presently disclosed resin shaped product that can
advantageously solve the problems set forth above is obtained
through melt shaping of any one of the shaping materials set forth
above.
[0029] The presently disclosed shaping material has excellent
crystallinity and is suitable for melt shaping because it rapidly
crystallizes upon cooling from a molten state. Moreover, a resin
shaped product having excellent mechanical strength can be obtained
through melt shaping of the presently disclosed shaping material.
Furthermore, a cosmetic container and a semiconductor container
having excellent attributes can suitably be produced through any
one of the shaping materials set forth above.
[0030] In particular, a presently disclosed semiconductor container
preferably has a degree of crystallinity of 10% or more. A
semiconductor container having a degree of crystallinity of 10% or
more has excellent chemical resistance. Note that the "degree of
crystallinity" can be measured using an X-ray diffractometer.
[0031] Moreover, the present disclosure aims to advantageously
solve the problems set forth above by disclosing a method of
producing a semiconductor container comprising: a purification step
of holding a target resin including a crystalline alicyclic
structure-containing resin having a melting point Tm (.degree. C.)
of 200.degree. C. or higher in a purification temperature range of
not lower than 140.degree. C. and not higher than 300.degree. C.
for not less than 0.5 hours and not more than 100 hours to obtain a
purified target resin; and a shaping step of heating a
pre-crystallization shaping material including the purified target
resin to a higher temperature than the melting point Tm (.degree.
C.) to melt the pre-crystallization shaping material and
subsequently shaping the pre-crystallization shaping material while
holding the pre-crystallization shaping material in a
crystallization temperature range of not lower than
(Tm-140.degree.) C. and lower than the melting point Tm (.degree.
C.) to cause crystallization. The method of producing a
semiconductor container including the production steps set forth
above enables good production of a semiconductor container having
high heat resistance.
[0032] In the presently disclosed method of producing a
semiconductor container, content of chlorobenzene-soluble
components in the pre-crystallization shaping material used in the
shaping step is preferably 1,000 ppm or less as an
o-dichlorobenzene-equivalent value based on gas chromatography
analysis with o-dichlorobenzene as a standard substance.
[0033] When the content of chlorobenzene-soluble components in the
pre-crystallization shaping material is 1,000 ppm or less, it is
possible to efficiently produce a semiconductor container for which
the amount of evolved outgas is small.
Advantageous Effect
[0034] According to the present disclosure, it is possible to
provide a shaping material that contains a high-melting point resin
and has excellent formability.
[0035] Moreover, according to the present disclosure, it is
possible to provide a resin shaped product, a cosmetic container,
and a semiconductor container that are obtained through shaping of
a shaping material that contains a high-melting point resin and has
excellent formability.
[0036] Furthermore, according to the present disclosure, it is
possible to provide a method of producing the aforementioned
semiconductor container.
DETAILED DESCRIPTION
[0037] The presently disclosed shaping material can suitably be
used to produce the presently disclosed resin shaped product,
cosmetic container, and semiconductor container. Moreover, the
presently disclosed cosmetic container can suitably be used as a
container for holding cosmetics of various properties and forms.
Furthermore, the presently disclosed semiconductor container can
suitably be used to hold a semiconductor material, such as a
semiconductor wafer, that can be used in production of a
semiconductor device. Also, the presently disclosed semiconductor
container can favorably be produced using the presently disclosed
method of producing a semiconductor container.
[0038] The following provides a detailed description of the present
disclosure that is divided into sections relating to 1) a shaping
material, 2) a resin shaped product, 3) a cosmetic container, 4) a
semiconductor container, and 5) a method of producing a
semiconductor container.
[0039] 1) Shaping Material
[0040] The presently disclosed shaping material is a shaping
material that contains a crystalline alicyclic structure-containing
resin. Features of the presently disclosed shaping material are
that the crystalline alicyclic structure-containing resin has a
melting point of 200.degree. C. or higher, and content of
chlorobenzene-soluble components in the shaping material is 1,000
ppm or less as an o-dichlorobenzene-equivalent value based on gas
chromatography analysis with o-dichlorobenzene as a standard
substance.
[0041] (Crystalline Alicyclic Structure-Containing Resin)
[0042] The crystalline alicyclic structure-containing resin is a
polymer that is obtained through polymerization of a cycloolefin,
that has an alicyclic structure in molecules thereof, and that
displays crystallinity. In the following description, the
crystalline alicyclic structure-containing resin is also referred
to simply as "polymer (a)". When a polymer is said to "display
crystallinity" in the present specification, this means that a
melting point is detected when the polymer is measured by
differential scanning calorimetry (DSC) in accordance with JIS
K7121. Note that the "crystallinity" of the polymer is a
characteristic property of a polymer having a specific structure
that may be brought about by stereoregularity of polymer
chains.
[0043] --Polymer (.alpha.--
[0044] The polymer (.alpha.) is not specifically limited and may,
for example, be a hydrogenated product of a norbornene-based
ring-opened polymer. More specifically, the polymer (.alpha.) may
be a commonly known polymer such as a hydrogenated
dicyclopentadiene ring-opened polymer having syndiotactic
stereoregularity that is described in WO 2012/033076 A1, a
hydrogenated dicyclopentadiene ring-opened polymer having isotactic
stereoregularity that is described in JP 2002-249553 A, or a
hydrogenated norbornene ring-opened polymer that is described in JP
2007-16102 A.
[0045] The melting point of the polymer (.alpha.) is required to be
200.degree. C. or higher, is preferably 220.degree. C. or higher,
and is preferably 350.degree. C. or lower, more preferably
320.degree. C. or lower, and even more preferably 300.degree. C. or
lower. A shaping material containing a polymer (.alpha.) that has a
melting point within any of the ranges set forth above has good
formability. Moreover, it is easy to obtain a resin shaped product,
a cosmetic container, a semiconductor container, and the like
(hereinafter, also referred to as a "resin shaped product and the
like") having excellent properties using this shaping material.
[0046] In particular, the polymer (.alpha.) is preferably a
hydrogenated dicyclopentadiene ring-opened polymer having
syndiotactic stereoregularity (hereinafter, also referred to as
"polymer (.alpha.1)") because this makes it easy to obtain a resin
shaped product and the like having high heat resistance and
chemical resistance. The hydrogenated dicyclopentadiene ring-opened
polymer is a hydrogenated product of a ring-opened polymer
including a monomer unit derived from a dicyclopentadiene. The
percentage content of the monomer unit derived from the
dicyclopentadiene in the hydrogenated dicyclopentadiene ring-opened
polymer when the entire hydrogenated dicyclopentadiene ring-opened
polymer is taken to be 100 mass % is preferably more than 90 mass
%, and more preferably more than 95 mass %.
[0047] Although no specific limitations are placed on the degree of
stereoregularity of the polymer (.alpha.1), it is preferable that
the polymer (.alpha.1) has a high degree of stereoregularity
because this makes it easy to obtain a resin shaped product having
various excellent properties, and, more specifically, to obtain a
cosmetic container having excellent water resistance, chemical
resistance, and ease of wiping off oil content and a semiconductor
container having high heat resistance and chemical resistance.
[0048] Specifically, for repeating units obtained by performing
ring-opening polymerization of dicyclopentadiene to obtain a
ring-opened polymer and then performing hydrogenation of the
ring-opened polymer, the proportion of racemo diads is preferably
51% or more, more preferably 60% or more, and particularly
preferably 65% or more.
[0049] A higher proportion of racemo diads, and thus a higher
degree of syndiotactic stereoregularity means that a hydrogenated
dicyclopentadiene ring-opened polymer having a higher melting point
is obtained.
[0050] The proportion of racemo diads can be determined based on
.sup.13C-NMR measurement described in the EXAMPLES section of the
present specification.
[0051] The polymer (.alpha.1) can be produced by performing
ring-opening polymerization using a monomer composition containing
a dicyclopentadiene such as dicyclopentadiene,
methyldicyclopentadiene, or 5,6-dihydrodicyclopentadiene
(hereinafter, also referred to as "monomer composition (.alpha.1)")
to obtain a ring-opened polymer and then hydrogenating at least
some of the unsaturated bonds present in the ring-opened polymer.
When all monomers contained in the monomer composition (.alpha.1)
are taken to be 100 mass %, the percentage content of the
dicyclopentadiene is preferably more than 90 mass %, and more
preferably more than 95 mass %. No specific limitations are placed
on monomers other than the dicyclopentadiene that may be contained
in the monomer composition (.alpha.1) so long as they are
copolymerizable with the dicyclopentadiene. For example, a
norbornene, cycloolefin, or diene other than the dicyclopentadiene
may be contained in the monomer composition (.alpha.1).
[0052] Moreover, endo and exo stereoisomers exist for
dicyclopentadienes. The dicyclopentadiene contained in the monomer
composition (.alpha.1) may be an endo isomer or an exo isomer. Note
that the dicyclopentadiene may include just the endo isomer or may
include just the exo isomer. Alternatively, a stereoisomer mixture
of the endo isomer and the exo isomer in any ratio may be contained
in the monomer composition (.alpha.1) as the dicyclopentadiene. In
particular, it is preferable that either the endo isomer or the exo
isomer is a main component of the dicyclopentadiene because this
makes it easier to obtain a resin shaped product having various
excellent properties, and, more specifically, to obtain a cosmetic
container having excellent water resistance, chemical resistance,
and ease of wiping off oil content and a semiconductor container
having high heat resistance and chemical resistance. In other
words, when the content of all dicyclopentadiene contained in the
monomer composition (.alpha.1) is taken to be 100 mass %, the
proportion of either the endo isomer or the exo isomer is
preferably more than 50 mass %. Moreover, the proportion
constituted by a stereoisomer that is a main component of the
dicyclopentadiene contained in the monomer composition (.alpha.1)
is preferably 80 mass % or more, more preferably 90 mass % or more,
and even more preferably 95 mass % or more. Note that since the
endo isomer of a dicyclopentadiene is easier to synthesize than the
exo isomer, the proportion constituted by the endo isomer among the
dicyclopentadiene contained in the monomer composition (.alpha.1)
is preferably higher than the proportion constituted by the exo
isomer.
[0053] No specific limitations are placed on the ring-opening
polymerization catalyst used in synthesis of the polymer (.alpha.1)
other than being a catalyst with which ring-opening polymerization
of a dicyclopentadiene can be performed to obtain a ring-opened
polymer having syndiotactic stereoregularity. Examples of
preferable ring-opening polymerization catalysts include catalysts
that include a metal compound indicated by the following formula
(1).
M(NR.sup.1)X.sub.4-a(OR.sup.2).sub.a.L.sub.b (1)
[0054] In formula (1), M is a metal atom selected from transition
metals in group 6 of the periodic table, R.sup.1 is a phenyl group
that optionally has a substituent at one or more of the 3, 4, and 5
positions or a group represented by --CH.sub.2R.sup.3 (R.sup.3 is a
hydrogen atom, an optionally substituted alkyl group, or an
optionally substituted aryl group), R.sup.2 is a group selected
from an optionally substituted alkyl group and an optionally
substituted aryl group, X is a group selected from a halogen atom,
an optionally substituted alkyl group, an optionally substituted
aryl group, and an alkyl silyl group, and L is an electron donating
neutral ligand. Moreover, a is 0 or 1, and b is an integer of 0 to
2.
[0055] M is a transition metal atom in group 6 of the periodic
table (chromium, molybdenum, or tungsten), is preferably molybdenum
or tungsten, and is more preferably tungsten.
[0056] Although no specific limitations are placed on the carbon
number of the phenyl group of R.sup.1 that optionally has a
substituent at one or more of the 3, 4, and 5 positions, the carbon
number is normally 6 to 20, and preferably 6 to 15.
[0057] Examples of possible substituents include alkyl groups such
as a methyl group and an ethyl group; halogen atoms such as a
fluorine atom, a chlorine atom, and a bromine atom; and alkoxy
groups such as a methoxy group, an ethoxy group, and a propoxy
group.
[0058] Moreover, substituents present at two or more of the 3, 4,
and 5 positions may be bonded to each other to form a ring
structure.
[0059] The phenyl group optionally having a substituent at one or
more of the 3, 4, and 5 positions may, for example, be an
unsubstituted phenyl group; a monosubstituted phenyl group such as
a 4-methylphenyl group, a 4-chlorophenyl group, a 3-methoxyphenyl
group, a 4-cyclohexylphenyl group, or a 4-methoxyphenyl group; a
disubstituted phenyl group such as a 3,5-dimethylphenyl group, a
3,5-dichlorophenyl group, a 3,4-dimethylphenyl group, or a
3,5-dimethoxyphenyl group; a trisubstituted phenyl group such as a
3,4,5-trimethylphenyl group or a 3,4,5-trichlorophenyl group; or an
optionally substituted 2-naphthyl group such as a 2-naphthyl group,
a 3-methyl-2-naphthyl group, or a 4-methyl-2-naphthyl group.
[0060] In the group of R.sup.1 that is represented by
--CH.sub.2R.sup.3, R.sup.3 is a group selected from a hydrogen
atom, an optionally substituted alkyl group, and an optionally
substituted aryl group.
[0061] Although no specific limitations are placed on the carbon
number of the optionally substituted alkyl group of R.sup.3, the
carbon number is normally 1 to 20, and preferably 1 to 10. The
alkyl group may be a linear alkyl group or a branched alkyl
group.
[0062] Examples of possible substituents include optionally
substituted phenyl groups such as a phenyl group and a
4-methylphenyl group; and alkoxy groups such as a methoxy group and
an ethoxy group.
[0063] The optionally substituted alkyl group of R.sup.3 may, for
example, be a methyl group, an ethyl group, a propyl group, an
isopropyl group, an n-butyl group, an isobutyl group, a t-butyl
group, a pentyl group, a neopentyl group, a benzyl group, a neophyl
group, or the like.
[0064] Although no specific limitations are placed on the carbon
number of the optionally substituted aryl group of R.sup.3, the
carbon number is normally 6 to 20, and preferably 6 to 15.
[0065] Examples of possible substituents include alkyl groups such
as a methyl group and an ethyl group; halogen atoms such as a
fluorine atom, a chlorine atom, and a bromine atom; and alkoxy
groups such as a methoxy group, an ethoxy group, and an isopropoxy
group.
[0066] The optionally substituted aryl group of R.sup.3 may, for
example, be a phenyl group, a 1-naphthyl group, a 2-naphthyl group,
a 4-methylphenyl group, a 2,6-dimethylphenyl group, or the
like.
[0067] Of these examples, the group represented by R.sup.3 is
preferably an alkyl group having a carbon number of 1 to 20.
[0068] Examples of the halogen atom of X include a chlorine atom, a
bromine atom, and an iodine atom.
[0069] Examples of the optionally substituted alkyl group and the
optionally substituted aryl group of X include the same examples as
given for the optionally substituted alkyl group and the optionally
substituted aryl group of R.sup.3.
[0070] Examples of the alkyl silyl group of X include a
trimethylsilyl group, a triethylsilyl group, and a
t-butyldimethylsilyl group.
[0071] In a case in which the metal compound indicated by formula
(1) includes two or more X groups, these groups may be bonded to
each other to form a ring structure.
[0072] Examples of the optionally substituted alkyl group and the
optionally substituted aryl group of R.sup.2 include the same
examples as given for the optionally substituted alkyl group and
the optionally substituted aryl group of R.sup.3.
[0073] The electron donating neutral ligand of L may, for example,
be an electron donating ligand that includes an atom from group 15
or 16 of the periodic table. Specific examples include phosphines
such as trimethylphosphine, triisopropylphosphine,
tricyclohexylphosphine, and triphenylphosphine; ethers such as
diethyl ether, dibutyl ether, 1,2-dimethoxyethane, and
tetrahydrofuran; and amines such as trimethylamine, triethylamine,
pyridine, and lutidine. Of these examples, ethers are
preferable.
[0074] The metal compound indicated by formula (1) is preferably a
tungsten compound that includes a phenylimide group (compound for
which M is a tungsten atom and R.sup.1 is a phenyl group in formula
(1)), and is more preferably a tetrachlorotungsten phenylimide
(tetrahydrofuran) complex.
[0075] No specific limitations are placed on the method by which
the metal compound indicated by formula (1) is synthesized and a
method described in JP H5-345817 A, for example, may be used.
Specifically, the target metal compound can be synthesized by
mixing an oxyhalide of a group 6 transition metal, a phenyl
isocyanate optionally having a substituent at one or more of the 3,
4, and 5 positions or a monosubstituted methyl isocyanate, an
electron donating neutral ligand (L), and, as necessary, an
alcohol, metal alkoxide, or metal aryloxide.
[0076] After synthesis of the metal compound, the reaction liquid
may be used as obtained as a catalyst solution for a ring-opening
polymerization reaction or the metal compound may be isolated and
purified by commonly known purification treatment such as
crystallization and then the obtained metal compound may be used in
a ring-opening polymerization reaction.
[0077] The ring-opening polymerization catalyst may be composed of
just the metal compound indicated by formula (1) or may be a
combination of the metal compound indicated by formula (1) and an
organometallic reducing agent. The use of a combination of the
metal compound indicated by formula (1) and an organometallic
reducing agent improves polymerization activity.
[0078] The organometallic reducing agent may, for example, be an
organometallic compound of any of groups 1, 2, 12, 13, and 14 of
the periodic table that includes a hydrocarbon group having a
carbon number of 1 to 20.
[0079] Examples of the organometallic compound include an
organolithium such as methyllithium, n-butyllithium, or
phenyllithium; an organomagnesium such as butylethylmagnesium,
butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride,
n-butylmagnesium chloride, or allylmagnesium bromide; an organozinc
such as dimethylzinc, diethylzinc, or diphenylzinc; an
organoaluminum such as trimethylaluminum, triethylaluminum,
triisobutylaluminum, di ethyl aluminum chloride, ethyl aluminum
sesquichloride, ethylaluminum dichloride, diethylaluminumethoxide,
diisobutylaluminum isobutoxide, ethylaluminum diethoxide, or
isobutylaluminum diisobutoxide; and an organotin such as
tetramethyltin, tetra(n-butyl)tin, or tetraphenyltin.
[0080] Of these examples, an organoaluminum or an organotin is
preferable.
[0081] The ring-opening polymerization reaction is normally carried
out in an organic solvent. No specific limitations are placed on
the organic solvent that is used other than being a solvent in
which a ring-opened polymer or hydrogenated product thereof can be
dissolved or dispersed under certain conditions and that does not
interfere with the ring-opening polymerization reaction or a
hydrogenation reaction.
[0082] Examples of organic solvents that may be used include
aliphatic hydrocarbons such as pentane, hexane, and heptane;
alicyclic hydrocarbons such as cyclopentane, cyclohexane,
methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane,
ethylcyclohexane, diethylcyclohexane, decahydronaphthalene,
bicycloheptane, tricyclodecane, hexahydroindene, and cyclooctane;
aromatic hydrocarbons such as benzene, toluene, and xylene;
halogenated aliphatic hydrocarbons such as dichloromethane,
chloroform, and 1,2-dichloroethane; halogenated aromatic
hydrocarbons such as chlorobenzene and dichlorobenzene;
nitrogen-containing hydrocarbons such as nitromethane,
nitrobenzene, and acetonitrile; ethers such as diethyl ether and
tetrahydrofuran; and mixed solvents that are a combination of any
of the preceding examples.
[0083] Of these organic solvents, aromatic hydrocarbons, aliphatic
hydrocarbons, alicyclic hydrocarbons, and ethers are
preferable.
[0084] The ring-opening polymerization reaction can be initiated by
mixing the monomer(s), the metal compound indicated by formula (1),
and, as necessary, the organometallic reducing agent. No specific
limitations are placed on the order in which these components are
added. For example, a solution containing the metal compound
indicated by formula (1) and the organometallic reducing agent may
be added to and mixed with a solution containing the monomer(s), a
solution containing the monomer(s) and the metal compound indicated
by formula (1) may be added to and mixed with a solution containing
the organometallic reducing agent, or a solution containing the
metal compound indicated by formula (1) may be added to and mixed
with a solution containing the monomer(s) and the organometallic
reducing agent.
[0085] Addition of each of the components may be performed by
adding all of the component at once or by dividing the component
between a plurality of additions. Moreover, addition may be
performed continuously over a relatively long time period (for
example, 1 minute or longer).
[0086] The monomer concentration at the start of the ring-opening
polymerization reaction is not specifically limited but is normally
1 mass % to 50 mass %, preferably 2 mass % to 45 mass %, and more
preferably 3 mass % to 40 mass %. Productivity may decrease if the
monomer concentration is too low, whereas solution viscosity after
the ring-opening polymerization reaction may be too high and the
subsequent hydrogenation reaction may become difficult if the
monomer concentration is too high.
[0087] The amount of the metal compound indicated by formula (1)
that is used in the ring-opening polymerization reaction is
normally an amount such that a molar ratio of "metal
compound:monomer" is 1:100 to 1:2,000,000, preferably 1:500 to
1:1,000,000, and more preferably 1:1,000 to 1:500,000. Removal of
the metal compound after the reaction may become difficult if the
amount of the metal compound is too large, whereas sufficient
polymerization activity may not be obtained if the amount of the
metal compound is too small.
[0088] In a case in which the organometallic reducing agent is
used, the amount thereof per 1 mol of the metal compound indicated
by formula (1) is preferably 0.1 mol to 100 mol, more preferably
0.2 mol to 50 mol, and particularly preferably 0.5 mol to 20 mol.
Polymerization activity may not be sufficiently improved if the
amount of the organometallic reducing agent that is used is too
small, whereas side reactions may occur more easily if the amount
of the organometallic reducing agent that is used is too large.
[0089] An activity modifier may be added to the polymerization
reaction system. The use of an activity modifier can stabilize the
ring-opening polymerization catalyst and adjust the reaction rate
of the ring-opening polymerization reaction and the molecular
weight distribution of the polymer.
[0090] The activity modifier may be any organic compound having a
functional group without any specific limitations. For example, the
activity modifier may be an oxygen-containing compound, a
nitrogen-containing compound, or a phosphorus-containing
compound.
[0091] Examples of oxygen-containing compounds that may be used
include ethers such as diethyl ether, diisopropyl ether, dibutyl
ether, anisole, furan, and tetrahydrofuran; ketones such as
acetone, benzophenone, and cyclohexanone; and esters such as ethyl
acetate.
[0092] Examples of nitrogen-containing compounds that may be used
include nitriles such as acetonitrile and benzonitrile; amines such
as triethylamine, triisopropylamine, quinuclidine, and
N,N-diethylaniline; and pyridines such as pyridine, 2,4-lutidine,
2,6-lutidine, and 2-t-butylpyridine.
[0093] Examples of phosphorus-containing compounds that may be used
include phosphines such as triphenylphosphine,
tricyclohexylphosphine, triphenyl phosphate, and trimethyl
phosphate; and phosphine oxides such as triphenylphosphine
oxide.
[0094] One activity modifier may be used individually, or two or
more activity modifiers may be used in combination. The amount of
the activity modifier that is added is not specifically limited and
may normally be selected from a range of 0.01 mol % to 100 mol %
relative to the metal compound indicated by formula (1).
[0095] A molecular weight modifier may be added to the
polymerization reaction system in order to adjust the molecular
weight of the ring-opened polymer. Examples of molecular weight
modifiers that may be used include .alpha.-olefins such as
1-butene, 1-pentene, 1-hexene, and 1-octene; aromatic vinyl
compounds such as styrene and vinyltoluene; oxygen-containing vinyl
compounds such as ethyl vinyl ether, isobutyl vinyl ether, allyl
glycidyl ether, allyl acetate, allyl alcohol, and glycidyl
methacrylate; halogen-containing vinyl compounds such as allyl
chloride; nitrogen-containing vinyl compounds such as acrylamide;
non-conjugated dienes such as 1,4-pentadiene, 1,4-hexadiene,
1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and
2,5-dimethyl-1,5-hexadiene; and conjugated dienes such as
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, and 1,3-hexadiene.
[0096] One molecular weight modifier may be used individually, or
two or more molecular weight modifiers may be used in
combination.
[0097] The amount of the molecular weight modifier that is added
may be set as appropriate depending on the target molecular weight
and may normally be selected from a range of 0.1 mol % to 50 mol %
relative to dicyclopentadiene.
[0098] The polymerization temperature is not specifically limited
but is normally within a range of -78.degree. C. to +200.degree.
C., and preferably within a range of -30.degree. C. to +180.degree.
C. The polymerization time is not specifically limited and depends
on the scale of reaction, but is normally within a range of 1
minute to 1,000 hours.
[0099] Although no specific limitations are placed on the
weight-average molecular weight (Mw) of the ring-opened polymer of
the dicyclopentadiene, the weight-average molecular weight (Mw) is
normally 1,000 to 1,000,000, and preferably 2,000 to 500,000. By
subjecting the ring-opened polymer having such a weight-average
molecular weight to a hydrogenation reaction, it is possible to
obtain a polymer (.alpha.1) having an excellent balance of shaping
processability, chemical resistance, and so forth. The
weight-average molecular weight of the ring-opened polymer can be
adjusted by adjusting the additive amount of the molecular weight
modifier used in polymerization, for example.
[0100] Although no specific limitations are placed on the molecular
weight distribution (Mw/Mn) of the ring-opened polymer of the
dicyclopentadiene, the molecular weight distribution (Mw/Mn) is
normally 1.0 to 4.0, and preferably 1.5 to 3.5. By subjecting the
ring-opened polymer having such a molecular weight distribution to
a hydrogenation reaction, it is possible to obtain a polymer
(.alpha.1) having excellent shaping processability. The molecular
weight distribution of the ring-opened polymer can be adjusted
through the addition method and the concentration of the monomer(s)
in the polymerization reaction.
[0101] The weight-average molecular weight (Mw) and the molecular
weight distribution (Mw/Mn) of the ring-opened polymer of the
dicyclopentadiene are taken to be polystyrene-equivalent values
that are measured by gel permeation chromatography (GPC) using
tetrahydrofuran as a developing solvent.
[0102] Through this ring-opening polymerization reaction, it is
possible to obtain a ring-opened polymer of the dicyclopentadiene
having syndiotactic stereoregularity. When reaction conditions in a
hydrogenation reaction carried out after the ring-opening
polymerization reaction are appropriately set, the tacticity of the
ring-opened polymer does not normally change through this
hydrogenation reaction. Therefore, the target polymer (.alpha.1)
can be obtained by subjecting the ring-opened polymer of the
dicyclopentadiene having syndiotactic stereoregularity to the
hydrogenation reaction. The degree of syndiotactic stereoregularity
of the ring-opened polymer can be adjusted by selecting the type of
ring-opening polymerization catalyst or altering the amount of the
ring-opening polymerization catalyst that is used. For example,
using a smaller amount of the ring-opening polymerization catalyst
tends to increase syndiotactic stereoregularity.
[0103] The hydrogenation reaction of the ring-opened polymer can be
carried out by supplying hydrogen into the reaction system in the
presence of a hydrogenation catalyst. The hydrogenation catalyst
may be a commonly known homogeneous catalyst or heterogeneous
catalyst that is used as a hydrogenation catalyst for olefin
compounds.
[0104] Examples of homogeneous catalysts that may be used include
catalysts composed of a combination of a transition metal compound
and an organoaluminum compound such as cobalt
acetate/triethylaluminum and nickel
acetylacetonate/triisobutylaluminum; catalysts composed of a
combination of a transition metal compound and an organoalkali
metal compound such as titanocene dichloride/n-butyllithium and
zirconocene dichloride/sec-butyllithium; catalysts composed of a
combination of a transition metal compound and an organomagnesium
compound such as tetrabutoxytitanate/dimethylmagnesium; and
precious metal complex catalysts such as
bis(triphenylphosphine)palladium dichloride,
chlorohydridocarbonyltris(triphenylphosphine)ruthenium,
chlorohydridocarbonylbis(tricyclohexylphosphine)ruthenium,
bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride,
and tris(triphenylphosphine)rhodium chloride.
[0105] Examples of heterogeneous catalysts that may be used include
metal catalysts such as nickel, palladium, platinum, rhodium, and
ruthenium; and solid catalysts having any of these metals supported
on a support (for example, carbon, silica, diatomaceous earth,
alumina, or titanium oxide) such as nickel/silica,
nickel/diatomaceous earth, nickel/alumina, palladium/carbon,
palladium/silica, palladium/diatomaceous earth, and
palladium/alumina.
[0106] The hydrogenation reaction is normally carried out in an
inert organic solvent. Examples of inert organic solvents that may
be used include aromatic hydrocarbons such as benzene and toluene;
aliphatic hydrocarbons such as pentane and hexane; alicyclic
hydrocarbons such as cyclohexane and decahydronaphthalene; and
ethers such as tetrahydrofuran and ethylene glycol dimethyl
ether.
[0107] The inert organic solvent may be the same solvent as used in
the ring-opening polymerization reaction or may be a different
solvent. Moreover, the hydrogenation reaction may be carried out by
adding the hydrogenation catalyst to the ring-opening
polymerization reaction liquid as obtained.
[0108] Although the reaction conditions of the hydrogenation
reaction differ depending on the hydrogenation catalyst that is
used, the reaction temperature is normally-20.degree. C. to
+250.degree. C., preferably -10.degree. C. to +220.degree. C., and
more preferably 0.degree. C. to +200.degree. C. The reaction rate
may become too slow if the reaction temperature is too low, whereas
side reactions may occur if the reaction temperature is too
high.
[0109] The hydrogen pressure is normally 0.01 MPa to 20 MPa,
preferably 0.05 MPa to 15 MPa, and more preferably 0.1 MPa to 10
MPa. The reaction rate may be too slow if the hydrogen pressure is
too low, whereas special equipment such as a reactor having high
pressure resistance may be required if the hydrogen pressure is too
high.
[0110] The reaction time is not specifically limited so long as the
desired percentage hydrogenation is reached, but is normally 0.1
hours to 10 hours. The target polymer (.alpha.1) may be collected
by a standard method after the hydrogenation reaction. Moreover,
the collected polymer (.alpha.1) may be dried by a standard
method.
[0111] Although no specific limitations are placed on the
percentage hydrogenation (proportion of unsaturated bonds that are
hydrogenated) in the hydrogenation reaction, the percentage
hydrogenation is preferably 98% or more, and more preferably 99% or
more. Heat resistance of the polymer (.alpha.1) tends to improve
with increasing percentage hydrogenation. The percentage
hydrogenation can be measured by .sup.1H-NMR.
[0112] In the present disclosure, the polymer (.alpha.) may be one
type of polymer used individually or two or more types of polymers
used in combination.
[0113] --Compound (.beta.)--
[0114] The presently disclosed shaping material may further contain
a compound (.beta.) that is a compound that differs from the
polymer (.alpha.) in terms of chemical composition and properties
and that also differs from other components such as additives
described further below.
[0115] The compound ((3) may, for example, be an impurity such as
residual monomer from synthesis of the polymer (.alpha.) or a
reaction solvent used in the polymerization reaction or
hydrogenation reaction in synthesis of the polymer (.alpha.). In a
case in which such impurities have a melting point, the melting
point may be lower than the melting point of the polymer (.alpha.).
It is preferable that the content of the compound (.beta.) in the
shaping material is extremely small. Crystallization of the shaping
material becomes easier when the content of the compound (.beta.)
in the shaping material is small. Moreover, mechanical strength of
an obtained resin shaped product or the like can be increased and
the amount of outgas can be reduced when the amount of the compound
(.beta.) in the shaping material is small.
[0116] --Other Components--
[0117] The presently disclosed shaping material may optionally
contain other components such as additives depending on the
application. Examples of additives that may be used include
antioxidants, crystal nucleating agents, waxes, ultraviolet
absorbers, light stabilizers, near-infrared absorbers, colorants
such as dyes and pigments, plasticizers, antistatic agents,
fluorescent whitening agents, and conductive materials. For
example, in a case in which the shaping material is to be used in
production of a cosmetic container, it is preferable that an
antioxidant, a crystal nucleating agent, a wax, and the like are
compounded as additives. Moreover, in a case in which the shaping
material is to be used in production of a semiconductor container,
for example, it is preferable that an antioxidant, a crystal
nucleating agent, a conductive material, and the like are
compounded as additives. The following provides specific examples
of some of these additives.
[0118] Examples of antioxidants that may be used include phenolic
antioxidants, phosphoric antioxidants, and sulfuric
antioxidants.
[0119] Examples of phenolic antioxidants include
3,5-di-t-butyl-4-hydroxytoluene,
2,2'-methylenebis(6-t-butyl-4-methylphenol),
4,4'-butylidenebis(6-t-butyl-3-methylphenol),
4,4'-thiobis(6-t-butyl-3-methylphenol), .alpha.-tocopherol,
2,2,4-trimethyl-6-hydroxy-7-t-butylchromane,
tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e, and pentaerythritol
tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].
[0120] Examples of phosphoric antioxidants include distearyl
pentaerythritol diphosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,
tris(2,4-di-t-butylphenyl) phosphite,
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenyl diphosphite, and
trinonylphenyl phosphite.
[0121] Examples of sulfuric antioxidants include distearyl
thiodipropionate and dilauryl thiodipropionate.
[0122] In a case in which the shaping material contains an
antioxidant, the content of the antioxidant is normally 0.01 mass %
to 10 mass %, and preferably 0.02 mass % to 5 mass % based on the
entire shaping material.
[0123] One antioxidant may be used individually, or two or more
antioxidants may be used in combination.
[0124] Examples of crystal nucleating agents that may be used
include sorbitol-based compounds, metal salts of organic phosphoric
acids, metal salts of organic carboxylic acids, kaolin, and
talc.
[0125] Examples of sorbitol-based compounds include dibenzylidene
sorbitol and diparamethyldibenzylidene sorbitol.
[0126] Examples of metal salts of organic phosphoric acids include
sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate and
bis(2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,2,3]dioxaphosp-
hocin-6-oxide) aluminum hydroxide.
[0127] Examples of metal salts of organic carboxylic acids include
sodium benzoate, potassium benzoate, calcium oxalate, and magnesium
stearate.
[0128] In a case in which the shaping material contains a crystal
nucleating agent, the content of the crystal nucleating agent is
normally 0.005 mass % to 10 mass %, and preferably 0.05 mass % to 5
mass % based on the entire shaping material.
[0129] Examples of waxes that may be used include petroleum-based
wax (paraffin wax, microcrystalline wax, or petrolatum),
Fischer-Tropsch wax, and polyalkylene wax.
[0130] In a case in which the shaping material contains a wax, the
content of the wax is normally 0.05 mass % to 20 mass %, and
preferably 0.5 mass % to 10 mass % based on the entire shaping
material.
[0131] Examples of conductive materials that may be used include,
but are not specifically limited to, conductive carbon materials
such as carbon black and carbon fiber, and metal materials such as
copper and aluminum. The amount of the conductive material is
normally 1 mass % to 20 mass % based on the entire shaping
material.
[0132] In a case in which the shaping material contains an additive
other than those listed above, the content of the additive can be
set as appropriate depending on the application.
[0133] In a case in which the shaping material contains additives,
the shaping material may be produced by a commonly known method
without any specific limitations.
[0134] For example, the shaping material containing the additives
can be produced by a method in which the additives are mixed with
the polymer (.alpha.1) after purification thereof, which is
described further below, or a method in which the additives are
mixed with the polymer (.alpha.) straight after production of the
polymer (.alpha.) and then the resultant shaping material is
subjected to purification.
[0135] The method by which the polymer (.alpha.) and the additives
are mixed in these production methods is preferably kneading in a
molten state.
[0136] The kneading can be performed using a melt-kneading machine
such as a single screw extruder, a twin screw extruder, a Banbury
mixer, a kneader, or a Feeder Ruder. The kneading temperature is
preferably within a range of 200.degree. C. to 400.degree. C., and
more preferably within a range of 240.degree. C. to 350.degree. C.
In the kneading, each of the components may be added all at once
and then kneaded or may be added as a number of portions while
being kneaded.
[0137] After the kneading, pelletization can be performed by a
standard method by extruding the kneaded product in a rod-like form
and cutting the kneaded product to an appropriate length using a
strand cutter.
[0138] [Amount of Chlorobenzene-Soluble Components]
[0139] When the shaping material is immersed in chlorobenzene to
obtain an extract containing eluted components from the shaping
material and then the amount of these eluted components is measured
by a specific method, the percentage content of the eluted
components in the shaping material is required to be 1,000 ppm or
less. The "specific method" referred to above is gas chromatography
analysis using o-dichlorobenzene as a standard substance.
[0140] The content of eluted components can be calculated as an
o-dichlorobenzene-equivalent value from a ratio of the area of
other peaks relative to the area of a peak for o-dichlorobenzene in
a gas chromatogram obtained by gas chromatography analysis. Note
that the main component among chlorobenzene-soluble components that
can be contained in the shaping material may be the previously
described compound (.beta.), for example.
[0141] The amount of chlorobenzene-soluble components as a
proportion relative to the entire shaping material, which can be
measured as described above, is required to be 1,000 ppm or less,
is preferably 500 ppm or less, and is more preferably 100 ppm or
less. Although the amount of chlorobenzene-soluble components is
preferably as small as possible and has no specific lower limit,
the amount is normally 0.1 ppm or more.
[0142] A shaping material in which the proportion of
chlorobenzene-soluble components is not more than any of the upper
limits set forth above has excellent formability and can
efficiently increase the degree of crystallinity of an obtained
shaped item. This can also increase mechanical strength, heat
resistance, and so forth of the obtained shaped item.
[0143] [Method of Reducing Amount of Chlorobenzene-Soluble
Components]
[0144] No specific limitations are placed on how the proportion of
chlorobenzene-soluble components is reduced.
[0145] For example, a shaping material for which the proportion of
eluted components is not more than any of the upper limits set
forth above can be efficiently obtained by performing purification
of the polymer (.alpha.) after it has been collected from the
reaction solution and undergone an optional drying step or of a
shaping material containing the polymer (.alpha.) and the
previously described optional additives (hereinafter, also referred
to collectively as the "crude polymer (.alpha.) or the like").
[0146] The purification may, for example, be heat treatment in
which the crude polymer (.alpha.) or the like is heated in a stream
of gas, in a liquid, or while in contact with a solid; extraction
treatment in which the crude polymer (.alpha.) or the like and an
extractant are brought into contact; reprecipitation treatment in
which the crude polymer (.alpha.) or the like is dissolved in a
suitable solvent and is then caused to reprecipitate; melting
treatment in which any of the preceding purification methods is
implemented after melting the crude polymer (.alpha.) or the like;
or the like.
[0147] These purification methods are commonly known methods. For
example, JP 2011-26614 A discloses a coagulation method and a
direct drying method as methods by which a volatile component such
as a solvent can be removed.
[0148] However, it is difficult to obtain a shaping material for
which the proportion of eluted components is not more than any of
the upper limits set forth above using the purification conditions
described in JP 2011-26614 A in the stated form, for example,
because it is not easy to reduce the content of the compound
(.beta.) contained in the crude polymer (.alpha.) or the like.
[0149] For this reason, it is important that purification is
carried out under conditions of higher temperature, longer
purification time, lower pressure, or the like compared to
conventional purification conditions.
[0150] Among the purification methods described above, purification
by a method in which the crude polymer (.alpha.) or the like is
heated for a long time is preferable because the proportion of
eluted components can be more efficiently reduced.
[0151] The heating temperature in this purification (purification
temperature) is normally not lower than 140.degree. C. and not
higher than 300.degree. C., and preferably not lower than
150.degree. C. and not higher than 250.degree. C., whereas the
heating time in this purification (purification time) is normally
not less than 0.5 hours and not more than 100 hours, and preferably
not less than 1 hour and not more than 48 hours. The pressure in
the purification may be a pressure corresponding to a standard
state in accordance with JIS Z 8703. Moreover, the atmosphere in
the purification may be an air atmosphere (for example, a standard
atmosphere in accordance with JIS W 0201) or may be an inert gas
atmosphere containing nitrogen gas and a noble gas such as argon
gas.
[0152] [Shaping Method of Shaping Material]
[0153] The alicyclic structure-containing resin contained in the
presently disclosed shaping material has excellent crystallinity
and has a characteristic of crystallizing in a short time upon
cooling from a molten state. Therefore, the presently disclosed
shaping material containing this alicyclic structure-containing
resin can suitably be used in melt shaping methods. Examples of
melt shaping methods include extrusion molding, injection molding,
melt spinning, press forming, blow molding, injection blow molding,
and calendering. Of these methods, injection molding is preferable
because it can sufficiently exploit the characteristics of the
presently disclosed shaping material.
[0154] The use of the presently disclosed shaping material in
injection molding enables stable production of a resin shaped
product in which crystallization has sufficiently progressed.
[0155] 2) Resin Shaped Product
[0156] The presently disclosed resin shaped product is a product
that is obtained through melt shaping of the presently disclosed
shaping material set forth above. The presently disclosed resin
shaped product has excellent mechanical strength since it is a melt
shaped item of the presently disclosed shaping material. This is
because the crystalline alicyclic structure-containing resin
contained in the presently disclosed shaping material has excellent
crystallinity, and thus a resin shaped product containing a resin
in which crystallization has sufficiently progressed can be
provided through melt shaping of the presently disclosed shaping
material.
[0157] Examples of melt shaping methods that can be used in
production of the presently disclosed resin shaped product include
the same shaping methods as given as examples of shaping methods in
the "Shaping method of shaping material" section of "1) Shaping
material". Of these shaping methods, injection molding is
preferable.
[0158] 3) Cosmetic Container
[0159] The presently disclosed cosmetic container is a shaped item
of the presently disclosed shaping material set forth above. More
specifically, the presently disclosed cosmetic container is a
shaped item of a shaping material that contains a crystalline
alicyclic structure-containing resin having a melting point of
200.degree. C. or higher and in which the content of
chlorobenzene-soluble components is 1,000 ppm or less as an
o-dichlorobenzene-equivalent value based on gas chromatography
analysis with o-dichlorobenzene as a standard substance.
Consequently, the presently disclosed cosmetic container has
excellent water resistance, chemical resistance, and ease of wiping
off oil content.
[0160] In particular, the cosmetic container has excellent water
resistance, chemical resistance, and ease of wiping off oil content
when the melting point of the crystalline alicyclic
structure-containing resin contained in the shaping material is
200.degree. C. or higher or satisfies any of the ranges set forth
above as preferable ranges for the "melting point of polymer
(.alpha.)".
[0161] Moreover, when the content of chlorobenzene-soluble
components in the shaping material as an
o-dichlorobenzene-equivalent value based on gas chromatography
analysis with o-dichlorobenzene as a standard substance is 1,000
ppm or less or satisfies any of the preferable upper limits set
forth above in the "Amount of chlorobenzene-soluble components"
section of "1) Shaping material", the degree of crystallinity of
the alicyclic structure-containing resin contained in the cosmetic
container can be sufficiently increased, and mechanical strength of
the cosmetic container can be increased.
[0162] [Production Method of Cosmetic Container]
[0163] Examples of melt shaping methods that can be used in
production of the presently disclosed cosmetic container include
the same shaping methods as given as examples of shaping methods in
the "Shaping method of shaping material" section of "1) Shaping
material". The shaping method can be selected as appropriate
depending on the shape of the target cosmetic container and so
forth.
[0164] [Shape of Cosmetic Container]
[0165] The presently disclosed cosmetic container may, for example,
be a pencil-type container, a jar-type container, or a tube-type
container.
[0166] The pencil-type container is, for example, a container in a
form like that of a writing instrument that includes, for example,
an outer tube that serves as a main body of the container, an inner
tube housed inside the outer tube, an applicator disposed at a tip
of the outer tube, and a cap that protects the applicator. A
cosmetic is normally housed directly inside the outer tube or
inside the inner tube. The pencil-type container can normally be
used to suitably house a cosmetic such as an eyeliner, eyebrow
cosmetic, or eyeshadow.
[0167] The pencil-type container can be produced by injection
molding, for example.
[0168] The jar-type container is, for example, a container that
includes a main body that is a pseudo-circular tube and a lid. A
cosmetic is housed inside the main body of the container. The
jar-type container can normally be used to suitably house a cream
or gel cosmetic.
[0169] The jar-type container can be produced by injection molding,
for example.
[0170] The tube-type container is, for example, a container that
includes a main body that is tube shaped and a lid. A cosmetic is
housed inside the main body of the container. The tube-type
container can normally be used to suitably house a cream or gel
cosmetic.
[0171] The main body of a tube-type container can normally be
produced by blow molding.
[0172] 4) Semiconductor Container
[0173] The presently disclosed semiconductor container is a shaped
item of the presently disclosed shaping material set forth above.
More specifically, the presently disclosed semiconductor container
is a shaped item of a shaping material that contains a crystalline
alicyclic structure-containing resin having a melting point of
200.degree. C. or higher and in which the content of
chlorobenzene-soluble components is 1,000 ppm or less as an
o-dichlorobenzene-equivalent value based on gas chromatography
analysis with o-dichlorobenzene as a standard substance.
Consequently, the presently disclosed semiconductor container has
excellent heat resistance.
[0174] In particular, when the content of chlorobenzene-soluble
components in the shaping material as an
o-dichlorobenzene-equivalent value based on gas chromatography
analysis with o-dichlorobenzene as a standard substance is 1,000
ppm or less or satisfies any of the preferable upper limits set
forth above in the "Amount of chlorobenzene-soluble components"
section of "1) Shaping material", the degree of crystallinity of
the alicyclic structure-containing resin forming the semiconductor
container can be sufficiently increased, and mechanical strength of
the semiconductor container can be increased. The
chlorobenzene-soluble components include content of the compound
(.beta.), which is inclusive of organic solvent used in synthesis
of the alicyclic structure-containing resin as previously
described. Accordingly, when a shaping material is said to contain
chlorobenzene-soluble components, this means that the shaping
material contains volatile components. Accordingly, outgassing may
occur if chlorobenzene-soluble components remain in the
semiconductor container (shaped item). This outgas becomes a cause
of contamination of contents (for example, a wafer) housed in the
semiconductor container. However, when the proportion of
chlorobenzene-soluble components in the shaping material is not
more than any of the upper limits set forth above, the amount of
outgas evolved from the semiconductor container decreases and
contamination of a wafer or the like can be inhibited. The yield in
semiconductor production can be improved as a result. Note that the
amount of outgas evolved from the semiconductor container can be
measured by a method described in the EXAMPLES section.
[0175] [Degree of Crystallinity of Semiconductor Container]
[0176] The semiconductor container preferably has a degree of
crystallinity of 10% or more. A degree of crystallinity of 10% or
more provides high chemical resistance (particularly resistance to
an oil/fat cleaning agent). The degree of crystallinity of the
semiconductor container is more preferably 15% or more, and even
more preferably 20% or more, and may normally be 50% or less from a
viewpoint of production efficiency. The degree of crystallinity of
the semiconductor container can be controlled by adjusting the
lower limit temperature of the crystallization temperature range
and the holding time in the shaping step of the subsequently
described method of producing a semiconductor container.
[0177] 5) Method of Producing Semiconductor Container
[0178] The presently disclosed semiconductor container set forth
above can be favorably produced by the presently disclosed method
of producing a semiconductor container. The presently disclosed
method of producing a semiconductor container includes a
purification step of holding a target resin including a crystalline
alicyclic structure-containing resin having a melting point Tm
(.degree. C.) of 200.degree. C. or higher in a purification
temperature range of not lower than 140.degree. C. and not higher
than 300.degree. C. for not less than 0.5 hours and not more than
100 hours to obtain a purified target resin (i.e., the "shaping
material" set forth above); and a shaping step of heating a
pre-crystallization shaping material including the purified target
resin to a higher temperature than the melting point Tm (.degree.
C.) to melt the pre-crystallization shaping material and
subsequently shaping the pre-crystallization shaping material while
holding the pre-crystallization shaping material in a
crystallization temperature range of not lower than
(Tm-140.degree.) C. and lower than the melting point Tm (.degree.
C.) to cause crystallization.
[0179] <Purification Step>
[0180] The purification step corresponds to the "method in which
the crude polymer (.alpha.) or the like is heated for a long time"
described in detail in the "Method of reducing amount of
chlorobenzene-soluble components" section. As previously defined,
the "crude polymer (.alpha.)" is a composition that may contain the
polymer (.alpha.), which is a crystalline alicyclic
structure-containing resin, and optional additives. Note that in a
case in which the purification step is implemented using a crude
polymer (.alpha.) with which additives have not been compounded as
the "target resin", an additive compounding step of compounding
additives with the purified target resin may be implemented at a
timing after the purification step and before the subsequently
described shaping step.
[0181] (Shaping Step)
[0182] In the shaping step, the pre-crystallization shaping
material obtained through the purification step and the optional
additive compounding step is melted and is then shaped into a
shaped item of a desired shape while being held in a
crystallization temperature range of not lower than
(Tm-140.degree.) C. and lower than the melting point Tm (.degree.
C.) to cause crystallization. The crystallization temperature range
may preferably be a temperature range of (Tm-125.degree.) C. or
higher, and more preferably (Tm-110.degree.) C. or higher. The
upper limit temperature of the crystallization temperature range is
lower than the melting point Tm (.degree. C.). The
pre-crystallization shaping material that has been melted by
heating to a higher temperature than the melting point Tm (.degree.
C.) starts to crystallize once the temperature drops below the
melting point Tm (.degree. C.) and falls to a crystallization onset
temperature after heating has stopped. The inventors discovered
that when the shaping material crystallizes at a temperature that
is not lower than any of the preferable lower limits for the
crystallization temperature range set forth above, the degree of
crystallinity of an obtained shaped item can be favorably
increased. Although the reason for this is not clear, it is
presumed to be due to the following characteristics of the shaping
material that were discovered by the inventors.
[0183] Firstly, studies carried out by the inventors revealed that
the shaping material set forth above readily crystallizes and
crystallization from a molten state tends to be completed in a
short time. As a result of further studies, the inventors
discovered that by causing the shaping material set forth above to
crystallize slowly in a comparatively high temperature range such
as set forth above, the degree of crystallinity of an obtained
shaped item can be significantly increased. For this reason, a
crystallization step performed under the conditions set forth above
is thought to enable efficient production of a semiconductor
container having a high degree of crystallinity.
[0184] The holding time under the temperature conditions set forth
above is preferably not less than 10 seconds and not more than 200
seconds. The degree of crystallinity of the obtained shaped item
can be favorably increased by setting the holding time as not less
than the lower limit set forth above.
[0185] Moreover, production efficiency of the semiconductor
container can be increased by setting the holding time as not more
than the upper limit set forth above.
[0186] The content of chlorobenzene-soluble components in the
pre-crystallization shaping material used in the shaping step is
preferably 1,000 ppm or less as an o-dichlorobenzene-equivalent
value based on gas chromatography analysis with o-dichlorobenzene
as a standard substance. The "content of chlorobenzene-soluble
components in the pre-crystallization shaping material" can be
measured by the method described in detail in the "Amount of
chlorobenzene-soluble components" section of the description
pertaining to 1) the shaping material, and preferred content ranges
therefor are also the same as set forth above. Production
efficiency of the semiconductor container can be improved when the
content of chlorobenzene-soluble components in the
pre-crystallization shaping material is 1,000 ppm or less.
Moreover, in a situation in which the obtained semiconductor
container is used, contamination of contents of the semiconductor
container, such as a wafer, due to outgas evolved from the
semiconductor container can be inhibited and the yield in
semiconductor production can be improved when the content of
chlorobenzene-soluble components in the pre-crystallization shaping
material is 1,000 ppm or less.
[0187] The presently disclosed method of producing a semiconductor
container including the various steps set forth above may, for
example, be a shaping method that is the same as any of the various
shaping methods given as examples in the "Shaping method of shaping
material" section of "1) Shaping material". Of these methods,
injection molding is preferably adopted in the method of producing
a semiconductor container.
[0188] In a case in which the presently disclosed method of
producing a semiconductor container is an injection molding method,
the lower limit of the crystallization temperature range can be
controlled by adjusting the temperature of a mold (for example, a
metal mold) used in injection molding. In other words, the target
semiconductor container can be obtained by heating the mold used in
injection molding to (Tm-140.degree.) C. or higher, preferably
(Tm-135.degree.) C. or higher, and more preferably (Tm-120.degree.)
C. or higher, subsequently injecting the molten pre-crystallization
shaping material, holding for a specific time, and then removing
the product from the mold. Note that the temperature of the mold
used in injection molding may be lower than the melting point Tm
(.degree. C.). For example, the semiconductor container can be
obtained by, in injection molding using a metal mold, injecting the
pre-crystallization shaping material into the metal mold while in a
molten state, shaping the shaping material into a desired shape
inside the mold while holding the shaping material in a
crystallization temperature range of not lower than
(Tm-140.degree.) C. and lower than the melting point Tm (.degree.
C.) to cause crystallization of the shaping material, and
subsequently removing the product from the mold.
EXAMPLES
[0189] The following provides a more specific description of the
present disclosure based on examples. However, the present
disclosure is not limited to the following examples. In the
following description, "%" and "parts" used in expressing
quantities are by mass, unless otherwise specified. Moreover, in
the case of a polymer that is produced through copolymerization of
a plurality of types of monomers, the proportion constituted by a
monomer unit in the polymer that is formed through polymerization
of a given monomer is normally, unless otherwise specified, the
same as the ratio (charging ratio) of the given monomer among all
monomers used in polymerization of the polymer. Note that pressures
in the following description are gauge pressures.
[0190] The following methods were used to measure various physical
properties in the examples and comparative examples.
[0191] (1) Molecular Weight (Weight-Average Molecular Weight and
Number-Average Molecular Weight) of Ring-Opened Polymer
[0192] Each produced solution containing a ring-opened polymer was
sampled to obtain a measurement sample. The obtained measurement
sample was used to determine the molecular weight of the
ring-opened polymer as a polystyrene-equivalent value using an
H-type column (produced by Tosoh Corporation) in a gel permeation
chromatography (GPC) system HLC-8320 (produced by Tosoh
Corporation) at a temperature of 40.degree. C. and with
tetrahydrofuran as a solvent.
[0193] (2) Percentage Hydrogenation in Hydrogenation Reaction
[0194] The percentage hydrogenation in a hydrogenation reaction was
determined by .sup.1H-NMR measurement using
orthodichlorobenzene-d.sub.4 as a solvent.
[0195] (3) Glass-Transition Temperature and Melting Point of
Alicyclic Structure-Containing Resin
[0196] A produced alicyclic structure-containing resin was used as
a measurement sample. The measurement sample was heated to
320.degree. C. under a nitrogen atmosphere and was then rapidly
cooled to room temperature at a cooling rate of -10.degree. C./min
using liquid nitrogen. A differential scanning calorimeter (DSC)
was used to heat the measurement sample at 10.degree. C./min and
determine the glass-transition temperature and melting point of the
alicyclic structure-containing resin.
[0197] (4) Proportion of Racemo Diads in Alicyclic
Structure-Containing Resin
[0198] A produced alicyclic structure-containing resin was used as
a measurement sample. The proportion of racemo diads was determined
by performing .sup.13C-NMR measurement by an inverse-gated
decoupling method at 200.degree. C. with
orthodichlorobenzene-d.sub.4/1,2,4-trichlorobenzene-d.sub.3
(TCB-d.sub.3) (mixing ratio (by mass): 1/2) as a solvent.
Specifically, the proportion of racemo diads was determined based
on an intensity ratio of a signal at 43.35 ppm attributed to meso
diads and a signal at 43.43 ppm attributed to racemo diads with a
peak at 127.5 ppm for orthodichlorobenzene-d.sub.4 taken as a
standard shift.
[0199] (5) Amount of Chlorobenzene-Soluble Components (Originating
from Cyclohexane/Toluene)
[0200] A produced shaping material was immersed in chlorobenzene
and orthodichlorobenzene was also added as an internal standard to
obtain an immersion liquid. The immersion liquid containing the
shaping material was stirred for 3 hours at 140.degree. C. in order
that chlorobenzene-soluble components contained in the shaping
material were extracted into the chlorobenzene. The obtained
extract was measured by a gas chromatograph under the following
conditions and the amount of chlorobenzene-soluble components in
the specimen was determined from an area ratio of peaks attributed
to chlorobenzene-soluble components and an internal standard peak.
Note that the chlorobenzene-soluble components contained in the
shaping material were components originating from solvent
components such as cyclohexane and toluene used in synthesis of the
alicyclic structure-containing resin.
[0201] In Table 2, the amount of a chlorobenzene-soluble component
calculated based on a peak corresponding to cyclohexane is
indicated in a row for component A and the amount of a
chlorobenzene-soluble component calculated based on a peak
corresponding to methylcyclohexane (hydrogenated product of toluene
contained in polymerization catalyst solution) is indicated in a
row for component B.
[0202] Moreover, in Tables 5 and 7, the amount of
chlorobenzene-soluble components indicates the amount of all
chlorobenzene-soluble components contained in the shaping material
(substantially equivalent to the amount of components calculated
based on both a peak corresponding to cyclohexane and a peak
corresponding to methylcyclohexane).
<Gas Chromatograph Measurement Conditions>
[0203] Apparatus: HP6850A produced by The Hewlett-Packard Company
(thermal conductivity detector)
[0204] Column: HP1 (internal diameter: 0.32 mm; length: 30 m; film
thickness: 0.25 .mu.m)
[0205] Oven temperature conditions: Held at 40.degree. C. for 6
minutes, subsequently raised to 240.degree. C. at a heating rate of
10.degree. C./min, and then raised to 300.degree. C. at a heating
rate of 30.degree. C./min
[0206] Injection port temperature: 160.degree. C.
[0207] Interface: 250.degree. C.
[0208] Pressure: 58.6 kPa
[0209] (6) Crystallization Peak Temperature
[0210] A differential scanning calorimeter (DSC) was used to heat
pellets (shaping material) to 320.degree. C. under a nitrogen
atmosphere and then cool the pellets to 40.degree. C. while
determining a peak temperature associated with crystallization. A
shaping material having a higher crystallization peak temperature
readily crystallizes in a higher temperature region and has better
crystallinity.
[0211] (7) Formability
[0212] Specimens for flexural modulus measurement were produced by
altering the cooling time of a mold when obtaining injection molded
items through shaping of a shaping material. The presence of
deformation in each specimen was checked after the specimen had
been removed from the mold. Formability of the shaping material was
then evaluated by the following standard.
[0213] A: Specimen without deformation obtained with cooling time
of less than 20 seconds
[0214] B: Specimen without deformation obtained with cooling time
of not less than 20 seconds and less than 30 seconds
[0215] C: Specimen without deformation obtained with cooling time
of not less than 30 seconds and less than 40 seconds
[0216] D: Specimen without deformation obtained with cooling time
of 40 seconds or more
[0217] (8) Flexural Modulus
[0218] An obtained shaping material was shaped, was loaded into a
small-size injection molding machine (Micro Injection Molding
Machine 10 cc produced by DSM Xplore), and was injection molded
under conditions of a molding temperature of 290.degree. C., an
injection pressure of 0.7 MPa, and a mold temperature of
170.degree. C. to produce a specimen for flexural modulus
measurement having a length of 80 mm, a width of 10 mm, and a
thickness of 4 mm. The cooling time of the mold when obtaining this
specimen was 60 seconds. The flexural modulus was measured by using
the obtained specimen to perform a flexural test in accordance with
JIS K7171 at a test rate of 2 mm/min using an AUTOGRAPH (product
name: AGS-5kNJ TCR2; produced by Shimadzu Corporation). A shaping
material having a high flexural modulus has high mechanical
strength.
[0219] (9) Water Resistance of Cosmetic Container
[0220] Cosmetic containers produced in Example 2 and Comparative
Example 2 were each weighed to determine the mass W.sub.0 of the
container, and then 5 mL of purified water was added into the
cosmetic container and was left for 1 week at 50.degree. C. with a
lid on the cosmetic container. Thereafter, the purified water in
the container was disposed of, the container was dried, and the
mass W.sub.1 of the container after drying was weighed. The
percentage mass loss was calculated by a formula:
(W.sub.0-W.sub.1)/W.sub.0.times.100. Water resistance was evaluated
by the following standard.
[0221] A: Percentage mass loss of less than 0.1%
[0222] B: Percentage mass loss of not less than 0.1% and less than
1.0%
[0223] C: Percentage mass loss of not less than 1.0% and less than
5.0%
[0224] D: Percentage mass loss of not less than 5.0% and less than
10%
[0225] E: Percentage mass loss of 10% or more
[0226] Note that evaluations of A to C in the water resistance test
and the chemical resistance test described below indicate adequate
performance as a cosmetic container.
[0227] (10) Chemical Resistance of Cosmetic Container
[0228] Chemical resistance was evaluated by the same standard as
for the water resistance test with the exception that ethanol,
glycerin, oleic acid, and liquid paraffin were used instead of the
purified water in the water resistance test described above.
[0229] (11) Ease of Wiping Off Oil Content from Cosmetic
Container
[0230] Skin cream (product name: Nivea Creme; produced by Nivea-Kao
Co., Ltd.) was applied onto the surfaces of cosmetic containers
produced in Example 2 and Comparative Example 2 and was left for 48
hours at 25.degree. C.
[0231] The skin cream was then wiped off using dry cotton for
cosmetics and the condition of the surface at this time was
inspected. Ease of wiping off oil content was evaluated by the
following standard.
[0232] A: Easily removed without a stain remaining on the
surface
[0233] B: Difficult to remove by wiping and a stain tends to remain
on the surface
[0234] (12) Degree of Crystallinity
[0235] A specimen was obtained by cutting out 20 mm.times.20 mm
from a smooth surface of a semiconductor container obtained in each
of Example 3 and Comparative Example 3. The degree of crystallinity
of the obtained specimen was measured by an X-ray diffractometer
(D8 DISCOVER produced by Bruker Corporation).
[0236] (13) Chemical Resistance
[0237] Specimens were obtained by cutting out 20 mm.times.20 mm
from a smooth surface of a semiconductor container obtained in each
of Example 3 and Comparative Example 3. The specimens were each
weighed to obtain the pre-immersion mass W.sub.0. The obtained
specimens were then immersed in chemicals under conditions shown in
Table 1 and were then each weighed to obtain the post-immersion
mass W.sub.1. Note that HC-FX50 produced by Tosoh Corporation was
used as an oil/fat cleaning agent.
[0238] The percentage mass loss was calculated from the
pre-immersion mass and the post-immersion mass of the specimen by a
formula: (W.sub.0-W.sub.1)/W.sub.0.times.100, and was evaluated by
the following standard.
[0239] A: Percentage mass loss of less than 0.1%
[0240] B: Percentage mass loss of not less than 0.1% and less than
0.2%
[0241] C: Percentage mass loss of 0.2% or more
TABLE-US-00001 TABLE 1 Chemical Temperature (.degree. C.) Time
(min) Hydrofluoric acid/nitric acid/ 25 10 acetic acid mixed
solution (mass ratio 1:3:8) 25% NaOH aqueous solution 40 10 Oil/fat
cleaning agent 40 10
[0242] (14) Amount of Outgas
[0243] A sample was obtained by cutting out 20 mm.times.20 mm of a
smooth surface of a semiconductor container obtained in each of
Example 3 and Comparative Example 3. A sample container made of a
glass tube of 4 mm in internal diameter into which the specimen had
been placed and a gas collection tube cooled by liquid nitrogen
were connected, the sample container was heated for 30 minutes at
180.degree. C. in a stream of high-purity helium (helium purity:
99.99995 volume %), and gas evolved from the sample was
continuously collected in the gas collection tube. Thermal
desorption gas chromatography mass spectrometry of the collected
gas was performed using n-decane as an internal standard and the
amount of gas evolved from the sample was calculated as an
n-decane-equivalent value.
[0244] This analysis was performed using the following apparatus
and analysis conditions.
[Thermal Desorption]
[0245] Apparatus: TDS A2 produced by Gerstel K.K. Japan
[0246] Sample heating conditions: 180.degree. C., 30 minutes
[0247] Helium gas flow rate: 30 mL/min
[0248] Gas collection tube: Tube of 1 mm in diameter packed with
glass wool
[0249] Temperature of gas collection tube: -130.degree. C. (during
gas collection), 280.degree. C. (during gas release)
[Gas Chromatography]
[0250] Apparatus: 6890N produced by Agilent Technologies, Inc.
[0251] Column: HP-5 ms (0.25.times.30 m, df=0.25 .mu.m) produced by
Agilent Technologies, Inc.
[0252] Carrier gas flow rate: 1 mL/min
[0253] Column pressure: None (flow control)
[0254] Heating profile: Held at 40.degree. C. for 3 minutes,
subsequently raised to 280.degree. C. at a heating rate of
10.degree. C./min, and then held at 280.degree. C. for 10
minutes
[Mass Spectrometer]
[0255] Apparatus: 5973N produced by Agilent Technologies, Inc.
[0256] (15) Heat Resistance
[0257] A wafer that had been heated to 180.degree. C. was placed in
the semiconductor container obtained in each of Example 3 and
Comparative Example 3 and was left until the wafer temperature
reached 25.degree. C.
[0258] The semiconductor container was inspected by eye before and
after the wafer was left, and heat resistance was evaluated in
accordance with the following standard.
[0259] A: No change in shape or color of semiconductor container
observed
[0260] B: Slight change in shape and/or color of semiconductor
container observed
[0261] C: Change in shape and/or color of semiconductor container
observed
Example 1 and Comparative Example 1
Production Example A
[Production of Alicyclic Structure-Containing Resin (A)]
[0262] A metal pressure-resistant reactor that had been internally
purged with nitrogen was charged with 154.5 parts of cyclohexane as
an organic solvent, 42.8 parts (30 parts in terms of
dicyclopentadiene) of a cyclohexane solution (concentration: 70%)
of dicyclopentadiene (endo isomer content ratio: 99% or more) as a
dicyclopentadiene, and 1.9 parts of 1-hexene as a molecular weight
modifier. The contents of the pressure-resistant reactor were
heated to 53.degree. C. Meanwhile, a ring-opening polymerization
catalyst solution was prepared by adding 0.061 parts of an n-hexane
solution (concentration: 19%) of diethylaluminum ethoxide
(organometallic reducing agent) as a ring-opening polymerization
catalyst to a solution obtained through dissolution of 0.014 parts
of a tetrachlorotungsten phenylimide (tetrahydrofuran) complex
(metal compound) as a ring-opening polymerization catalyst in 0.70
parts of toluene (organic solvent), and then performing mixing for
10 minutes. This ring-opening polymerization catalyst solution was
added into the reactor and a ring-opening polymerization reaction
was carried out for 4 hours at 53.degree. C. to obtain a solution
containing a dicyclopentadiene ring-opened polymer.
[0263] The polymerization reaction was stopped by adding 0.037
parts of 1,2-ethanediol as an inhibitor to 200 parts of the
obtained solution containing the dicyclopentadiene ring-opened
polymer and performing stirring for 1 hour at 60.degree. C.
Thereafter, 1 part of a hydrotalcite-like compound (product name:
KYOWAAD.RTM. 2000 (KYOWAAD is a registered trademark in Japan,
other countries, or both); produced by Kyowa Chemical Industry Co.,
Ltd.) was added as an adsorbent, heating was performed to
60.degree. C., and stirring was performed for 1 hour. Next, 0.4
parts of a filter aid (product name: Radiolite.RTM. #1500
(Radiolite is a registered trademark in Japan, other countries, or
both); produced by Showa Chemical Industry Co., Ltd.) was added and
the adsorbent was filtered off using a PP pleated cartridge filter
(product name: TCP-HX; produced by Toyo Roshi Kaisha, Ltd.) to
obtain a solution containing the dicyclopentadiene ring-opened
polymer.
[0264] A portion of this solution was used to measure the molecular
weight of the dicyclopentadiene ring-opened polymer. The
weight-average molecular weight (Mw) was 28,100, the number-average
molecular weight (Mn) was 8,750, and the molecular weight
distribution (Mw/Mn) was 3.21.
[0265] Next, 100 parts of cyclohexane and 0.0043 parts of
chlorohydridocarbonyltris(triphenylphosphine)ruthenium were added
to 200 parts of the obtained solution containing the
dicyclopentadiene ring-opened polymer (polymer content: 30 parts),
and a hydrogenation reaction was carried out for 4 hours at a
hydrogen pressure of 6 MPa and a temperature of 180.degree. C. The
reaction liquid was a slurry in which solid content had
precipitated.
[0266] Solid content and solution were separated through
centrifugal separation of the reaction liquid and then the solid
content was dried under reduced pressure at 60.degree. C. for 24
hours to obtain 28.5 parts of a hydrogenated dicyclopentadiene
ring-opened polymer (alicyclic structure-containing resin (A)).
[0267] The percentage hydrogenation of unsaturated bonds in the
hydrogenation reaction was 99% or more. The hydrogenated
dicyclopentadiene ring-opened polymer had a glass-transition
temperature of 98.degree. C. and a melting point of 262.degree. C.
The proportion of racemo diads was 89%.
[0268] [Production of Shaping Material (1-1)]
--Purification Step--
[0269] The alicyclic structure-containing resin (A) obtained as
described above was used as a target resin and was dried under a
nitrogen atmosphere (inert gas atmosphere) at a purification
temperature of 200.degree. C. for a purification time of 24 hours
to obtain a purified alicyclic structure-containing resin (A)
(i.e., a purified target resin).
[0270] --Shaping Step of Pelletized Shaping Material--
[0271] A mixture was obtained by mixing 0.8 parts of an antioxidant
(tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]metha-
ne; product name: Irganox.RTM. 1010 (Irganox is a registered
trademark in Japan, other countries, or both); produced by BASF
Japan Ltd.) relative to 100 parts of the purified alicyclic
structure-containing resin (A) obtained in the purification step,
and was loaded into a twin screw extruder (TEM-37B produced by
Toshiba Machine Co., Ltd.). The mixture was hot melt-extruded and
was shaped into a strand-form shaped product that was subsequently
cut by a strand cutter to obtain a pelletized shaping material
(1-1).
[0272] The operating conditions of the twin screw extruder were as
follows. [0273] Barrel temperature setting: 270.degree. C. to
280.degree. C. [0274] Die temperature setting: 250.degree. C.
[0275] Screw rotation speed: 145 rpm [0276] Feeder rotation speed:
50 rpm
Example 1-1
[0277] The pelletized shaping material (1-1) obtained according to
Production Example A was used to measure or evaluate the amount of
chlorobenzene-soluble components, the crystallization peak
temperature, formability, and the flexural modulus as previously
described. The results are shown in Table 2.
Examples 1-2 and 1-3 and Comparative Examples 1-1 to 1-3
[0278] An alicyclic structure-containing resin (A) obtained
according to the method described in the "Production of alicyclic
structure-containing resin (A)" section of Production Example A was
purified with the purification temperature and purification time
shown in Table 2. Measurements and evaluations were made in the
same manner as in Example 1-1. The results are shown in Table
2.
TABLE-US-00002 TABLE 2 Example 1 Comparative Example 1 1 2 3 1 2 3
Type of crystalline alicyclic A A A A A A structure-containing
resin Production Purification Atmosphere Nitrogen Nitrogen Nitrogen
Nitrogen Nitrogen Nitrogen process conditions Purification 200 170
150 100 130 100 temperature (.degree. C.) Purification 24 10 10 10
10 48 time (hr) Shaping Amount of Component 30 400 500 1000 800 400
material chlorobenzene- A (ppm) soluble Component 30 100 400 1000
400 700 components B (ppm) Total (ppm) 60 500 900 2000 1200 1100
Crystallization peak 185 181 175 165 168 167 temperature (.degree.
C.) Evaluation Formability A A B D C C Flexural modulus (MPa) 2800
2780 2710 2420 2510 2490
[0279] It can be seen from Table 2 that the shaping materials
according to Examples 1-1 to 1-3, which each contained a
crystalline alicyclic structure-containing resin (A) having a
melting point of 200.degree. C. or higher and had a content of
chlorobenzene-soluble components of 1,000 ppm or less as measured
by the prescribed method, had excellent formability. On the other
hand, it can be seen that formability was inadequate in the case of
the shaping materials according to Comparative Examples 1-1 to 1-3
in which the same crystalline alicyclic structure-containing resin
(A) as in Examples 1-1 to 1-3 was used, but different purification
conditions were adopted and the content of chlorobenzene-soluble
components exceeded 1,000 ppm.
Example 2 and Comparative Example 2
[0280] An alicyclic structure-containing resin (A) and a shaping
material (1-1) containing this alicyclic structure-containing resin
(A) that were obtained according to the previously described
Production Example A, and alicyclic structure-containing resins (B)
to (F) and shaping materials (2-2) to (2-9) containing these
alicyclic structure-containing resins (B) to (F) that were obtained
as described below were used in Example 2 and Comparative Example
2.
[0281] [Production of Alicyclic Structure-Containing Resin (B)]
[0282] The alicyclic structure-containing resin (B) was produced in
the same manner as in the method described in the "Production of
alicyclic structure-containing resin (A)" section of Production
Example A with the exception that the amount of tetrachlorotungsten
phenylimide (tetrahydrofuran) complex used as a ring-opening
polymerization catalyst was changed to 0.038 parts.
[0283] [Production of Alicyclic Structure-Containing Resin (C)]
[0284] The alicyclic structure-containing resin (C) was produced in
the same manner as in the method described in the "Production of
alicyclic structure-containing resin (A)" section of Production
Example A with the exception that the amount of tetrachlorotungsten
phenylimide (tetrahydrofuran) complex used as a ring-opening
polymerization catalyst was changed to 0.053 parts.
[0285] [Production of Alicyclic Structure-Containing Resin (D)]
[0286] The alicyclic structure-containing resin (D) was produced
according to a method described in "Production Example 1" of JP
2015-160399 A.
[0287] The specific procedure was as follows.
[0288] In a reactor, 0.82 parts of 1-hexene, 0.15 parts of dibutyl
ether, and 0.30 parts of triisobutylaluminum were added to 500
parts of dehydrated cyclohexane at room temperature under a
nitrogen atmosphere and were mixed therewith. Thereafter, 76 parts
of dicyclopentadiene (DCPD), 70 parts of
8-methyl-tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodec-3-ene (TCD),
54 parts of
tetracyclo[7.4.0.0.sup.2,7.1.sup.10,13]tridec-2,4,6,11-tetraene
(MTF), and 80 parts of tungsten hexachloride (0.7% toluene
solution) were continuously added over 2 hours, concurrently to one
another, while maintaining the temperature at 45.degree. C. to
carry out polymerization. Next, 1.06 parts of butyl glycidyl ether
and 0.52 parts of isopropyl alcohol were added to the
polymerization solution to deactivate the polymerization catalyst
and stop the polymerization reaction. The polymerization conversion
rate of monomers determined by analyzing the obtained reaction
solution containing a ring-opened polymer by gas chromatography was
99.5%.
[0289] Next, 270 parts of cyclohexane was added to 100 parts of the
obtained reaction solution containing the ring-opened polymer, 5
parts of diatomaceous earth-supported nickel catalyst (proportion
of supported nickel: 58 mass %; pore volume: 0.25 mL/g; specific
surface area: 180 m.sup.2/g) was further added as a hydrogenation
catalyst, the pressure was raised to 5 MPa with hydrogen and the
temperature was raised to 200.degree. C. under stirring, and then a
reaction was carried out for 8 hours to obtain a reaction solution
containing a hydrogenated DCPD/TCD/MTF ring-opened copolymer. The
hydrogenation catalyst was removed by filtration and then
cyclohexane (solvent) and other volatile components were removed
from the solution at a temperature of 270.degree. C. and a pressure
of 1 kPa using a cylindrical evaporator (produced by Hitachi,
Ltd.). Next, the hydrogenated product was extruded from an extruder
in a molten state as strands that were subsequently cooled and then
pelletized to obtain pellets. The pelletized hydrogenated
ring-opened copolymer (alicyclic structure-containing resin (D))
had a Mw of 34,000, a percentage hydrogenation of 99% or more, and
a glass-transition temperature of 135.degree. C.
[0290] [Production of Alicyclic Structure-Containing Resin (E)]
[0291] The alicyclic structure-containing resin (E) was produced
according to a method described in "Production Example 1" of JP
2008-137671 A.
[0292] The specific procedure was as follows.
[0293] In a reactor, 0.55 parts by mass of 1-hexene, 0.30 parts by
mass of diisopropyl ether, 0.20 parts by mass of
triisobutylaluminum, and 0.075 parts by mass of isobutyl alcohol
were added to 500 parts by mass of dehydrated cyclohexane at room
temperature under a nitrogen atmosphere and were mixed therewith.
Thereafter, 250 parts by mass of 2-norbornene (2-NB) and 15 parts
by mass of a 1.0 mass % toluene solution of tungsten hexachloride
were continuously added over 2 hours while maintaining the
temperature at 55.degree. C. to carry out polymerization. The
obtained ring-opened polymer had a weight-average molecular weight
(Mw) of 83,000 and a molecular weight distribution (Mw/Mn) of
1.8.
[0294] The polymerization reaction liquid containing the
ring-opened polymer that was obtained as described above was
transferred to a pressure-resistant hydrogenation reactor and 0.5
parts by mass of a diatomaceous earth-supported nickel catalyst
(T8400 produced by Nissan Sud-Chemie; proportion of supported
nickel: 58 mass %) was added thereto. A reaction was carried out
for 6 hours at a temperature of 160.degree. C. and a hydrogen
pressure of 4.5 MPa. The solution was filtered with diatomaceous
earth as a filter aid using a filtration device that included a
stainless steel screen to remove the catalyst.
[0295] The obtained reaction solution was poured into 3,000 parts
by mass of isopropyl alcohol under stirring to cause precipitation
of the hydrogenated product. The hydrogenated product was collected
by filtration, was washed with 500 parts by mass of acetone, and
was then dried for 48 hours at 0.13.times.10.sup.3 Pa in a vacuum
dryer set to 100.degree. C. to obtain 190 parts by mass of the
alicyclic structure-containing resin (E). The obtained alicyclic
structure-containing resin (E) had a percentage hydrogenation of
99% or more, a weight-average molecular weight (Mw) of 82,200, a
molecular weight distribution (Mw/Mn) of 2.9, and a melting point
of 140.degree. C.
[0296] [Production of Alicyclic Structure-Containing Resin (F)]
[0297] After 0.0068 parts of a molybdenum compound indicated by the
following general formula (X) had been added into a glass reactor
equipped with a stirrer, 24 parts of cyclohexane, 6 parts of
dicyclopentadiene, and 0.00573 parts of 1-hexene were added, and a
polymerization reaction was carried out at room temperature.
##STR00001##
[0298] The polymerization reaction liquid obtained after 3 hours of
this polymerization reaction was poured into an excess of
isopropanol. The polymer was caused to completely precipitate, and
was then filtered off and washed. The obtained filtration residue
was dried under reduced pressure at 40.degree. C. for 40 hours. The
obtained ring-opened polymer had a weight-average molecular weight
(Mw) of 103,000 and a number-average molecular weight (Mn) of
37,000.
[0299] Next, an autoclave equipped with a stirrer was charged with
5.0 parts of the ring-opened polymer obtained as described above
and 88 parts of cyclohexane. A hydrogenation catalyst solution
containing 0.031 parts of bis(tricyclohexylphosphine)benzylidene
ruthenium(IV) dichloride and 1.8 parts of ethyl vinyl ether
dissolved in 18 parts of cyclohexane was subsequently added and a
hydrogenation reaction was carried out for 10 hours at a hydrogen
pressure of 0.785 MPa and a temperature of 120.degree. C. After
this reaction, the reaction liquid was poured into an excess of
isopropanol. The polymer was caused to completely precipitate, and
was then filtered off and washed. The obtained filtration residue
was dried under reduced pressure at 40.degree. C. for 40 hours. The
percentage hydrogenation was 99% or more. The obtained alicyclic
structure-containing resin (F) had a melting point of 272.degree.
C. and a glass-transition temperature of 102.degree. C.
[0300] Physical properties of the alicyclic structure-containing
resins (A) to (F) obtained as described above are shown in Table 3.
Note that the percentage content of DCPD in Table 3 indicates the
percentage content (mass %) of dicyclopentadiene units when all
repeating units included in the alicyclic structure-containing
resin are taken to be 100 mass %.
TABLE-US-00003 TABLE 3 Alicyclic structure-containing resin (A) (B)
(C) (D) (E) (F) Percentage content of 100 100 100 38 0 100 DCPD
(mass %) Melting point (.degree. C.) 262 260 256 -- 140 272
Glass-transition 98 97 96 135 -5 102 temperature (.degree. C.)
Proportion of 89 77 68 -- -- 5 racemodiads (%)
[0301] [Production of Shaping Materials (2-2) to (2-9)]
[0302] The shaping materials (2-2) to (2-9) were obtained through
the same procedure as that described in "Production of shaping
material (1-1)" with the exception that the alicyclic
structure-containing resins and additives indicated in Table 4 were
used.
[0303] The additives used in production of these shaping materials
were as follows.
[0304] Antioxidant (A):
Tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methan-
e; Irganox.RTM. 1010 (product name) produced by BASF Japan Ltd.
[0305] Antioxidant (B): Pentaerythritol
tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate];
Irganox.RTM. L101 (product name) produced by BASF Japan Ltd.
[0306] Crystal nucleating agent: Sodium
2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate: ADK STAB.RTM.
NA-11 (ADK STAB is a registered trademark in Japan, other
countries, or both) (product name) produced by ADEKA
Corporation
[0307] Wax: Paraffin wax; LUVAX-1266 (product name) produced by
Nippon Seiro Co., Ltd.
[0308] Thermoplastic elastomer: Block copolymer including aromatic
vinyl compound-based polymer block and isobutylene-based polymer
block (polymer obtained according to method described in Production
Example 4 of JP 2015-160399 A)
TABLE-US-00004 TABLE 4 Shaping material (1-1) (2-2) (2-3) (2-4)
(2-5) (2-6) (2-7) (2-8) (2-9) Alicyclic (A) 100 -- -- 100 100 -- --
-- -- structure- (B) -- 100 -- -- -- -- -- -- -- containing (C) --
-- 100 -- -- -- -- -- -- resin (parts) (D) -- -- -- -- -- 100 100
-- -- (E) -- -- -- -- -- -- -- 100 -- (F) -- -- -- -- -- -- -- --
100 Additives Antioxidant (A) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 --
Antioxidant (B) -- -- -- -- -- -- -- -- -- Crystal -- -- -- 0.4 0.2
-- -- -- -- nucleating agent Wax -- -- -- -- 2 -- -- -- --
Thermoplastic -- -- -- -- -- -- -- -- -- elastomer Purification
atmosphere Nitrogen Nitrogen Nitrogen Nitrogen Nitrogen Nitrogen
Nitrogen Nitrogen Nitrogen Purification temperature 200 200 200 200
200 200 200 200 200 (.degree. C.) Purification time (hr) 24 24 24
24 24 24 24 24 24
Example 2-1
[0309] The pelletized shaping material (1-1) obtained as described
above was used to perform injection molding in an injection molding
machine (ROBOSHOT .alpha.100B produced by FANUC) with conditions of
a shaping temperature of 280.degree. C., a mold temperature of
160.degree. C., and a cooling time of resin in the mold of 60
seconds to produce a jar-type cosmetic container having an internal
capacity of 10 mL. Water resistance, chemical resistance, and ease
of wiping off oil content were evaluated for the produced cosmetic
container as previously described. The results are shown in Table
5.
Examples 2-2 to 2-6 and Comparative Examples 2-1 to 2-4
[0310] The same operations as in Example 2-1 were performed with
respect to the shaping materials (2-2) to (2-9) that were obtained
as previously described. However, the shaping conditions were
changed as indicated in Table 5. With the exception of in
Comparative Example 2-4, a cosmetic container was obtained. The
obtained cosmetic container was evaluated in the same manner as in
Example 2-1. The results are shown in Table 5.
[0311] In Comparative Example 2-4, however, a cosmetic container
could not be produced because progression of crystallization in
injection molding was too slow. For the alicyclic
structure-containing resin (F) used in Comparative Example 2-4, the
hydrogenated product was filtered and the resultant filtration
residue was dried under reduced pressure at 40.degree. C. for 40
hours in production as previously described. However, volatile
impurities could not be completely removed by drying under these
conditions and the shaping material (2-9) containing the alicyclic
structure-containing resin (F) had a large amount of residual
components (refer to Table 5).
TABLE-US-00005 TABLE 5 Example 2 Comparative Example 2 1 2 3 4 5 6
1 2 3 4 Shaping Type (1-1) (2-2) (2-3) (1-1) (2-4) (2-5) (2-6)
(2-7) (2-8) (2-9) material Amount of chlorobenzene- 60 140 100 60
70 70 50 80 900 2000 soluble components (ppm) Shaping Mold
temperature 160 160 160 80 145 150 80 80 120 160 conditions
(.degree. C.) Holding time (s) 60 60 60 60 60 60 60 60 60 60
Evaluation Water resistance A A A A A A A A A -- Chemical Ethanol B
B B B B A B B E -- resistance Glycerin A B B B A A B A B -- Oleic
acid A B C B A A E D A -- Liquid paraffin B C C B A A E E B -- Ease
of wiping off oil content A A A A A A B B B --
[0312] The following findings can be made from Tables 3 to 5.
Firstly, the cosmetic containers according to Examples 2-1 to 2-6,
which were each obtained using a shaping material that satisfied
the prescribed properties, had excellent water resistance, chemical
resistance, and ease of wiping off oil content. In particular, it
can be seen through comparison of Examples 2-1 and 2-4 that
chemical resistance can be increased by increasing the mold
temperature in injection molding. On the other hand, the cosmetic
containers of Comparative Examples 2-1 and 2-2 had poor chemical
resistance and ease of wiping off oil content because they
contained an amorphous alicyclic structure-containing resin (D).
Moreover, the cosmetic container of Comparative Example 2-3
contained a crystalline alicyclic structure-containing resin (E)
but the melting point thereof (140.degree. C.) was not high. As a
result, the obtained cosmetic container was easily eroded by
ethanol and had poor ease of wiping off oil content.
Example 3 and Comparative Example 3
[0313] An alicyclic structure-containing resin (A) obtained
according to the previously described Production Example A, a
shaping material (3-1) containing the alicyclic
structure-containing resin (A), alicyclic structure-containing
resins (B) to (F) obtained in the same way as in Example 2 and
Comparative Example 2, and shaping materials (3-2) to (3-10)
containing these alicyclic structure-containing resins (B) to (F)
were used in Example 3 and Comparative Example 3.
[0314] In production of the shaping materials (3-1) to (3-10), a
conductive agent shown below was used in addition to an antioxidant
(A), an antioxidant (B), and a crystal nucleating agent that were
the same as those used in the "Production of shaping materials
(2-2) to (2-9)" section of Example 2 and Comparative Example 2,
these additives were compounded with the alicyclic
structure-containing resins (A) to (F) in the ratios shown in Table
6, and purification was carried out under purification conditions
shown in Table 6. Note that a purification step was not implemented
in production of the shaping materials (3-8) and (3-10).
TABLE-US-00006 TABLE 6 Shaping material (3-1) (3-2) (3-3) (3-4)
(3-5) (3-6) (3-7) (3-8) (3-9) (3-10) Alicyclic (A) 100 -- -- 100
100 -- -- -- -- 100 structure- (B) -- 100 -- -- -- -- -- -- -- --
containing (C) -- -- 100 -- -- -- -- -- -- -- resin (D) -- -- -- --
-- 100 -- -- -- -- (parts) (E) -- -- -- -- -- -- 100 -- -- -- (F)
-- -- -- -- -- -- -- 100 100 -- Additives Antioxidant 0.8 0.8 0.8
0.8 0.8 0.8 0.8 -- -- 0.8 (parts) (A) Antioxidant -- -- -- -- -- --
-- 0.2 0.2 -- (B) Crystal -- -- -- 0.4 -- -- -- -- -- -- nucleating
agent Conductive -- -- -- -- 10 -- -- -- -- -- agent Purification
atmosphere Air Air Air Air Air Air Air -- Air -- Purification
temperature (.degree. C.) 200 200 200 200 200 200 200 -- 200 --
Purification time (hr) 24 24 24 24 24 24 24 -- 24 --
Example 3-1
[0315] The shaping material (3-1) obtained as described above was
melted at a shaping temperature of 280.degree. C. and was used to
perform injection molding in an injection molding machine (ROBOSHOT
.alpha.100B produced by FANUC) under conditions of a mold
temperature of 160.degree. C. and a holding time of resin in the
mold of 60 seconds to produce a semiconductor container for a wafer
size of 300 mm. Various evaluations of the obtained semiconductor
container were performed according to the previously described
methods. The results are shown in Table 7.
Example 3-2 to Comparative Example 3-4
[0316] A semiconductor container was produced in the same way as in
Example 3-1 with the exception that injection molding was performed
under the conditions (mold temperature and holding time) shown in
Table 7. Various evaluations of the obtained semiconductor
container were performed according to the previously described
methods. The results are shown in Table 7. Note that in Comparative
Examples 3-3 and 3-4, it was not possible to obtain a shaped item
with the mold temperature set as 160.degree. C. and the holding
time set as 300 seconds.
TABLE-US-00007 TABLE 7 Example 3 Comparative Example 3 1 2 3 4 5 6
7 1 2 3 4 Shaping Type (3-1) (3-2) (3-3) (3-1) (3-4) (3-5) (3-9)
(3-6) (3-7) (3-8) (3-10) material Amount of 60 140 100 60 70 80 90
120 140 2000 1500 chlorobenzene-soluble components (ppm) Shaping
Mold temperature 160 160 160 130 160 160 160 130 40 160 160
conditions (.degree. C.) Holding time (s) 60 60 60 60 60 60 60 60
60 300 300 Evaluation Degree of crystallinity (%) 30 30 30 10 30 30
30 0 30 -- -- Heat resistance A A A A A A A B C -- -- Amount of
outgas (ppm) 70 85 75 70 70 80 90 70 90 -- -- Chemical Hydrofluoric
acid/ A A A A A A A A A -- -- resistance nitric acid/ acetic acid
mixed solution 25% NaOH A A A A A A A A A -- -- Oil/fat cleaning
agent A A A B A A A C A -- --
[0317] As is clear from Table 7, the semiconductor containers
obtained in Examples 3-1 to 3-7 had excellent heat resistance and
chemical resistance. Moreover, the semiconductor containers of
Examples 3-1 to 3-7 had an outgas amount of 90 ppm or less and
excellent cleanliness. Therefore, the probability of a wafer or the
like being contaminated when the wafer or the like is housed in any
of these semiconductor containers is low.
[0318] In particular, by comparing Example 3-1 and Example 3-4 with
reference to Table 7, it can be seen that the degree of
crystallinity of the obtained semiconductor container (shaped
product) could be increased and chemical resistance could be
improved by using a mold having a higher temperature.
[0319] On the other hand, it can be seen from Table 7 that the
semiconductor container of Comparative Example 3-1 had poor
chemical resistance and heat resistance compared to the
semiconductor containers of Examples 3-1 to 3-7 as a consequence of
containing an amorphous alicyclic structure-containing resin.
[0320] It can also be seen from Table 7 that although the
semiconductor container of Comparative Example 3-2 was crystalline,
the semiconductor container had poor heat resistance compared to
the semiconductor containers of Examples 3-1 to 3-7. By referring
to Tables 3 and 6, it can be seen that the semiconductor container
of Comparative Example 3-2 is a shaped item of the shaping material
(3-7), which contained the alicyclic structure-containing resin (E)
having a melting point of 140.degree. C. and a glass-transition
temperature of -5.degree. C. Therefore, the cause of low heat
resistance of the semiconductor container of Comparative Example
3-2 is thought to be that although the alicyclic
structure-containing resin (E) is crystalline, it has a low melting
point (140.degree. C.) and a low glass-transition temperature
(-5.degree. C.).
[0321] Moreover, it can be seen with reference to Comparative
Example 3-3 in Table 7 that the shaping material (3-8) containing
an alicyclic structure-containing resin (F) for which a
purification step had not been performed had a high content of
chlorobenzene-soluble components. In the production process of the
alicyclic structure-containing resin (F), an operation of drying
under reduced pressure at 40.degree. C. for 40 hours was performed
both at a point at which the ring-opened polymer was obtained and a
point after hydrogenation was completed. However, the value for the
amount of chlorobenzene-soluble components shown in Table 7
indicates that the amount of chlorobenzene-soluble components in
the shaping material could not be sufficiently reduced through this
operation of drying under reduced pressure. On the other hand, it
can be seen with reference to Example 3-7 in Table 7 that when the
shaping material (3-9) containing an alicyclic structure-containing
resin (F) for which a purification step had been performed was
used, a semiconductor container having a small amount of outgas and
excellent heat resistance and chemical resistance was obtained.
[0322] Furthermore, it can be seen with reference to Comparative
Example 3-4 in Table 7 that the shaping material (3-10) containing
an alicyclic structure-containing resin (A) for which a
purification step had not been performed had a high content of
chlorobenzene-soluble components.
INDUSTRIAL APPLICABILITY
[0323] According to the present disclosure, it is possible to
provide a shaping material that contains a high-melting point resin
and has excellent formability.
[0324] Moreover, according to the present disclosure, it is
possible to provide a resin shaped product, a cosmetic container,
and a semiconductor container that are obtained through shaping of
a shaping material that contains a high-melting point resin and has
excellent formability.
[0325] Furthermore, according to the present disclosure, it is
possible to provide a method of producing the aforementioned
semiconductor container.
* * * * *